Process for industrial production of an aromatic carbonate

ABSTRACT

It is an object of the present invention to provide a specific process that enables aromatic carbonates to be produced with high selectivity and high productivity stably for a prolonged period of time on an industrial scale of not less than 1 ton per hour from a dialkyl carbonate and an aromatic monohydroxy compound using two continuous multi-stage distillation columns. Although there have been various proposals regarding processes for the production of aromatic carbonates by means of a reactive distillation method, these have all been on a small scale and short operating time laboratory level, and there have been no disclosures whatsoever on a specific process or apparatus enabling mass production on an industrial scale. According to the present invention, there are provided two specified continuous multi-stage distillation columns, and there is also provided a specific process that enables aromatic carbonates to be produced with high selectivity and high productivity stably for a prolonged period of time on an industrial scale of not less than 1 ton per hour from a dialkyl carbonate and an aromatic monohydroxy compound using a apparatus in which these two continuous multi-stage distillation columns are connected together.

TECHNICAL FIELD

The present invention relates to an industrial process for theproduction of an aromatic carbonate. More particularly, the presentinvention relates to an industrial process for the production of a largeamount of an aromatic carbonate containing a diaryl carbonate as a mainproduct, which is useful as a raw material of a transesterificationmethod polycarbonate by subjecting a dialkyl carbonate and an aromaticmonohydroxy compound to transesterification reaction in two continuousmulti-stage distillation columns in each of which a catalyst is present.

BACKGROUND ART

An aromatic carbonates is important as a raw material for the productionof aromatic polycarbonate which is the most widely used engineeringplastic, without using toxic phosgene. As a process for producing anaromatic carbonate, a process of reacting an aromatic monohydroxycompound with phosgene has been known from long ago, and has also beenthe subject of a variety of studies in recent years. However, thisprocess has the problem of using phosgene, and in addition chlorinatedimpurities that are difficult to separate out are present in thearomatic carbonate produced using this process, and hence the aromaticcarbonate cannot be used as the raw material for the production of thearomatic polycarbonate. Because such chlorinated impurities markedlyinhibit the polymerization reaction in the transesterification methodwhich is carried out in the presence of an extremely small amount of abasic catalyst; for example, even if such chlorinated impurities arepresent in an amount of only 1 ppm, the polymerization hardly proceedsat all. To make the aromatic carbonate capable of being used as the rawmaterial of polycarbonate of the transesterification method, troublesomemulti-stage separation/purification processes such as enough washingwith a dilute aqueous alkaline solution and hot water, oil/waterseparation, distillation and so on are thus required. Furthermore, theyield of the aromatic carbonate decreases due to hydrolysis loss duringthis separation/purification processes. Therefore, there are manyproblems in carrying out this method economically on an industrialscale.

On the other hand, a process for producing aromatic carbonates throughtransesterification reactions between a dialkyl carbonate and anaromatic monohydroxy compound is also known. However, suchtransesterification reactions are all equilibrium reactions. Since theequilibriums are biased extremely toward the original system and thereaction rates are slow, and hence there have been many difficulties inproducing aromatic carbonates industrially in large amounts using thismethod. Several proposals have been made to improve on the abovedifficulties, but most of these have related to development of acatalyst to increase the reaction rate. Many metal compounds have beenproposed as catalysts for this type of transesterification reaction. Forexample, Lewis acids such as a transition metal halide and Lewisacid-forming compounds (see Patent Documents 1: Japanese PatentApplication Laid-Open No. 51-105032, Japanese Patent ApplicationLaid-Open No. 56-123948, Japanese Patent Application Laid-Open No.56-123949 (corresponding to West German Patent Application No. 2528412,British Patent No. 1499530, and U.S. Pat. No. 4,182,726), JapanesePatent Application Laid-Open No. 51-75044 (corresponding to West GermanPatent Application No. 2552907, and U.S. Pat. No. 4,045,464)), tincompounds such as an organo-tin alkoxide and an organo-tin oxides (seePatent Documents 2: Japanese Patent Application Laid-Open No. 54-48733(corresponding to West German Patent Application No. 2736062), JapanesePatent Application Laid-Open No. 54-63023, Japanese Patent ApplicationLaid-Open No. 60-169444 (corresponding to U.S. Pat. No. 4,554,110),Japanese Patent Application Laid-Open No. 60-169445 (corresponding toU.S. Pat. No. 4,552,704), Japanese Patent Application Laid-Open No.62-277345, Japanese Patent Application Laid-Open No. 1-265063, JapanesePatent Application Laid-Open No. 60-169444 (corresponding to U.S. Pat.No. 4,554,110), Japanese Patent Application Laid-Open No. 60-169445(corresponding to U.S. Pat. No. 4,552,704), Japanese Patent ApplicationLaid-Open No. 62-277345, Japanese Patent Application Laid-Open No.1-265063), salts and alkoxides of alkali metals and alkaline earthmetals (see Patent Document 3: Japanese Patent Application Laid-Open No.57-176932), lead compounds (see Patent Documents 4: Japanese PatentApplication Laid-Open No. 57-176932, Japanese Patent ApplicationLaid-Open No. 1-93560), complexes of metals such as copper, iron andzirconium (see Patent Document 5: Japanese Patent Application Laid-OpenNo. 57-183745), titanic acid esters (see Patent Documents 6: JapanesePatent Application Laid-Open No. 58-185536 (corresponding to U.S. Pat.No. 4,410,464), Japanese Patent Application Laid-Open No. 1-265062),mixtures of a Lewis acid and a protonic acid (see Patent Document 7:Japanese Patent Application Laid-Open No. 60-173016 (corresponding toU.S. Pat. No. 4,609,501)), compounds of Sc, Mo, Mn, Bi, Te or the like(see Patent Document 8: Japanese Patent Application Laid-Open No.1-265064), ferric acetate (see Patent Document 9: Japanese PatentApplication Laid-Open No. 61-172852), and so on have been proposed.However, the problem of the disadvantageous equilibrium cannot be solvedmerely by developing the catalyst, and hence there are very many issuesto be solved including the reaction system in order to provide a processfor the industrial production aiming for mass production.

Attempts have also been made to devise a reaction system so as to shiftthe equilibrium toward the product system as much as possible, and thusimprove the yield of the aromatic carbonates. For example, for thereaction between dimethyl carbonate and phenol, there have been proposeda method in which by-produced methanol is distilled off by azeotropytogether with an azeotrope-forming agent (see Patent Document 10:Japanese Patent Application Laid-Open No. 54-48732 (corresponding toWest German Patent Application No; 736063, and U.S. Pat. No.4,252,737)), and a method in which the methanol produced as theby-product is removed by being adsorbed onto a molecular sieve (seePatent Document 11: Japanese Patent Application Laid-Open No. 58-185536(corresponding to U.S. Pat. No. 410,464)). Moreover, a method has alsobeen proposed in which, using an apparatus in which a distillationcolumn is provided on top of a reactor, an alcohol produced as theby-product in the reaction is separated off from the reaction mixture,and at the same time unreacted starting material that evaporates isseparated off by distillation (see Patent Documents 12: examples inJapanese Patent Application Laid-Open No. 56-123948 (corresponding toU.S. Pat. No. 4,182,726), examples in Japanese Patent ApplicationLaid-Open No. 56-25138, examples in Japanese Patent ApplicationLaid-Open No. 60-169444 (corresponding to U.S. Pat. No. 4,554,110),examples in Japanese Patent Application Laid-Open No. 60-169445(corresponding to U.S. Pat. No. 4,552,704), examples in Japanese PatentApplication Laid-Open No. 60-173016 (corresponding to U.S. Pat. No.4,609,501), examples in Japanese Patent Application Laid-Open No.61-172852, examples in Japanese Patent Application Laid-Open No.61-291545, examples in Japanese Patent Application Laid-Open No.62-277345).

However, these reaction systems are basically batch system or switchoversystem. Because there is the limitation in the improvement of thereaction rate through catalyst development for such atransesterification reaction, and the reaction rate is still slow, andthus it has been thought that a batch system is preferable to acontinuous system. Of these, a continuous stirring tank reactor (CSTR)system in which a distillation column is provided on top of a reactorhas been proposed as a continuous system, but there are problems such asthe reaction rate being slow, and a gas-liquid interface in the reactorbeing small, based on the volume of the liquid. Hence it is not possibleto make the conversion high. Accordingly, it is difficult to attain theobject of producing the aromatic carbonate continuously in large amountsstably for a prolonged period of time by means of the above-mentionedmethods, and many issues remain to be resolved before economicalindustrial implementation is possible.

The present inventors have developed reactive distillation methods inwhich such a transesterification reaction is carried out in a continuousmulti-stage distillation column simultaneously with separation bydistillation, and have been the first in the world to disclose that sucha reactive distillation system is useful for such a transesterificationreaction, for example a reactive distillation method in which a dialkylcarbonate and an aromatic hydroxy compound are continuously fed into amulti-stage distillation column, and the reaction is carried outcontinuously inside the column in which a catalyst is present, whilecontinuously withdrawing a low boiling point component containing analcohol produced as a by-product by distillation and continuouslywithdrawing a component containing a produced alkyl aryl carbonate froma lower portion of the column (see Patent Document 13: Japanese PatentApplication Laid-Open No. 3-291257), a reactive distillation method inwhich an alkyl aryl carbonate is continuously fed into the multi-stagedistillation column, and the reaction is carried out continuously insidethe column in which a catalyst is present, while continuouslywithdrawing by distillation a low boiling point component containing adialkyl carbonate produced as a by-product and continuously withdrawinga component containing a produced diaryl carbonate from a lower portionof the column (see Patent Document 14: Japanese Patent ApplicationLaid-Open No. 4-9358), a reactive distillation method in which thesereactions are carried out using two continuous multi-stage distillationcolumns, and hence a diaryl carbonate is produced continuously whileefficiently recycling a dialkyl carbonate produced as a by-product (seePatent Document 15: Japanese Patent Application Laid-Open No. 4-211038),and a reactive distillation method in which a dialkyl carbonate and anaromatic hydroxy compound or the like are continuously fed into themulti-stage distillation column, and a liquid that flows down throughthe column is withdrawn from a side outlet provided at an intermediatestage and/or a lowermost stage of the distillation column, and isintroduced into a reactor provided outside the distillation column so asto bring about reaction, and is then introduced back in through acirculating inlet provided at a stage above the stage where the outletis provided, whereby reaction is carried out in both the reactor and thedistillation column (see Patent Documents 16: Japanese PatentApplication Laid-Open No. 4-224547, Japanese Patent ApplicationLaid-Open No. 4-230242, Japanese Patent Application Laid-Open No.4-235951).

These reactive distillation methods proposed by the present inventorsare the first to enable aromatic carbonates to be produced continuouslyand efficiently, and many similar reactive distillation systems based onthe above disclosures have been proposed thereafter (see PatentDocuments 17 to 32: Patent Document 17: International Publication No.00/18720 (corresponding to U.S. Pat. No. 5,362,901), Patent Document 18:Italian Patent No. 01255746, Patent Document 19: Japanese PatentApplication Laid-Open No. 6-9506 (corresponding to European Patent No.0560159, and U.S. Pat. No. 5,282,965), Patent Document 20: JapanesePatent Application Laid-Open No. 6-41022 (corresponding to EuropeanPatent No. 0572870, and U.S. Pat. No. 5,362,901), Patent Documents 21:Japanese Patent Application Laid-Open No. 6-157424 (corresponding toEuropean Patent No. 0582931, and U.S. Pat. No. 5,334,742), JapanesePatent Application Laid-Open No. 6-184058 (corresponding to EuropeanPatent No. 0582930, and U.S. Pat. No. 5,344,954), Patent Document 22:Japanese Patent Application Laid-Open No. 7-304713, Patent Document 23:Japanese Patent Application Laid-Open No. 9-40616, Patent Document 24:Japanese Patent Application Laid-Open No. 9-59225, Patent Document 25:Japanese Patent Application Laid-Open No. 9-110805, Patent Document 26:Japanese Patent Application Laid-Open No. 9-165357, Patent Document 27:Japanese Patent Application Laid-Open No. 9-173819, Patent Documents 28:Japanese Patent Application Laid-Open No. 9-176094, Japanese PatentApplication Laid-Open No. 2000-191596, Japanese Patent ApplicationLaid-Open No. 2000-191597, Patent Document 29: Japanese PatentApplication Laid-Open No. 9-194436 (corresponding to European Patent No.0785184, and U.S. Pat. No. 5,705,673), Patent Document 30: InternationalPublication No. 00/18720 (corresponding to U.S. Pat. No. 6,093,842),Patent Documents 31: Japanese Patent Application Laid-Open No.2001-64234, Japanese Patent Application Laid-Open No. 2001-64235, PatentDocument 32: International Publication No. 02/40439 (corresponding toU.S. Pat. Nos. 6,596,894, 6,596,895, and 6,600,061)).

Among reactive distillation systems, the present applicants have furtherproposed, as a method that enables highly pure aromatic carbonates to beproduced stably for a prolonged period of time without a large amount ofa catalyst being required, a method in which high boiling point materialcontaining a catalyst component is reacted with an active substance andthen separated off, and the catalyst component is recycled (see PatentDocuments 31: Japanese Patent Application Laid-Open No. 2001-64234,Japanese Patent Application Laid-Open No. 2001-64235), and a methodcarried out while keeping a weight ratio of a polyhydric aromatichydroxy compound in the reaction system to a catalyst metal at not morethan 2.0 (see Patent Document 32: International Publication No. 02/40439(corresponding to U.S. Pat. Nos. 6,596,894, 6,596,895, and 6,600,061)).Furthermore, the present inventors have proposed a method in which 70 to99% by weight of phenol produced as a by-product in a polymerizationprocess is used as a starting material, and diphenyl carbonate can beproduced by means of the reactive distillation method. This diphenylcarbonate can be used as the raw material for polymerization of aromaticpolycarbonates (see Patent Document 33: International Publication No.97/11049 (corresponding to European Patent No. 0855384, and U.S. Pat.No. 5,872,275)).

However, in all of these prior art documents in which the production ofaromatic carbonates using the reactive distillation method is proposed,there is no disclosure whatsoever of a specific process or apparatusenabling mass production on an industrial scale (e.g. not less than 1ton per hour), nor is there any description suggesting such a process orapparatus. For example, the descriptions regarding the heights (H₁ andH₂, respectively: cm), the diameters (D₁ and D₂, respectively: cm), thenumbers of stages (n₁ and n₂, respectively) of the pair of reactivedistillation columns and the feeding rates of the raw material (Q₁ andQ₂, respectively: kg/hr) disclosed for producing diphenyl carbonate(DPC) from dimethyl carbonate and phenol are as summarized in thefollowing table.

TABLE 1 PATENT DOCU- H₁ D₁ n₁ Q₁ H₂ D₂ n₂ Q₂ MENT 600 25 20 66 600 25 2023 15 350 2.8 — 0.2 305 5~10 15+ 0.6 21 PACK- ING 500 5 50 0.6 400 8 500.6 23 100 4 — 1.4 200 4 — 0.8 24 300 5 40 1.5 — 5 25 0.7 28 1200 20 4086 600 25 20 31 33 34 600 — 20 66 600 — 20 22 35See Patent Document 34: Japanese Patent Application Laid-Open No.11-92429 (corresponding to European Patent No. 1016648, and U.S. Pat.No. 6,262,210 See Patent document 35: Japanese Patent ApplicationLaid-Open No. 9-255772 (corresponding to European Patent No. 0892001,and U.S. Pat. No. 5,747,609)

In other words, a pair of the biggest continuous multi-stagedistillation columns used when carrying out this reaction using thereactive distillation system are those disclosed by the presentapplicants in Patent Documents 33 and 34. As can be seen from Table 1,the maximum values of the various conditions for the continuousmulti-stage distillation columns disclosed for the above reaction areH₁=1200 cm, H₂=600 cm, D₁=20 cm, D₂=25 cm, n₁=n₂=50 (Patent Document23), Q₁=86 kg/hr, and Q₂=31 kg/hr, and the amount of diphenyl carbonateproduced has not exceeded approximately 6.7 kg/hr, which is not anamount produced on an industrial scale.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a specific processthat enables aromatic carbonates containing a diaryl carbonate as a mainproduct to be produced with high selectivity and high productivitystably for a prolonged period of time on an industrial scale of not lessthan 1 ton per hour using two continuous multi-stage distillationcolumns from a dialkyl carbonate and an aromatic monohydroxy compound.

Since the present inventors disclosed a process for producing aromaticcarbonates using a continuous multi-stage distillation column, variousproposals regarding processes for the production of aromatic carbonatesby means of a reactive distillation method have been made. However,these have all been on a small scale and short operating time laboratorylevel, and there have been no disclosures whatsoever on a specificprocess or apparatus enabling mass production on an industrial scale. Inview of these circumstances, the present inventors carried out studiesaimed at discovering a specific process enabling an aromatic carbonatecontaining a diaryl carbonate as a main product to be produced with highselectivity and high productivity stably for a prolonged period of timeon an industrial scale of not less than 1 ton per hour. As a result, thepresent inventors have reached to the present invention.

That is, in the first aspect of the present invention, there isprovided:

-   1. A process for the production of an aromatic carbonate containing    a diaryl carbonate as a main product from a dialkyl carbonate and an    aromatic monohydroxy compound as a starting material, which    comprises the steps of:

(i) continuously feeding said starting material into a first continuousmulti-stage distillation column in which a catalyst is present;

(ii) carrying out the reaction in said first column to produce analcohol and an alkyl aryl carbonate;

(iii) continuously withdrawing a first column low boiling point reactionmixture containing a produced alcohol from an upper portion of saidfirst column in a gaseous form while continuously withdrawing a firstcolumn high boiling point reaction mixture containing an alkyl arylcarbonate from a lower portion of said first column in a liquid form;

(IV) continuously feeding said first column high boiling point reactionmixture into a second continuous multi-stage distillation column inwhich a catalyst is present and which is connected to said first columnwhile carrying out the reaction in said second column to produce adialkyl carbonate and a diaryl carbonate;

(V) continuously withdrawing a second column low boiling point reactionmixture containing said produced dialkyl carbonate from an upper portionof said second column in a gaseous form while continuously withdrawing asecond column high boiling point reaction mixture containing saidproduced diaryl carbonate from a lower portion of said second column ina liquid form; wherein

(a) a molar ratio of the dialkyl carbonate to the aromatic monohydroxycompound in said starting material which is fed continuously into saidfirst continuous multi-stage distillation column is in a range of from0.1 to 10;

(b) said first continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₁ (cm) and an inside diameter D₁ (cm),and having an internal with a number of stages n₁ thereinside, and has agas outlet having an inside diameter d₁₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₁₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₁ (cm) satisfies the following formula (1),1500≦L₁≦8000  (1),

(2) said inside diameter D₁ (cm) of the column satisfies the followingformula (2),100≦D₁≦2000  (2),

(3) a ratio of said length L₁ (cm) to said inside diameter D₁ (cm) ofthe column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3),

(4) said number of stages n₁ satisfies the following formula (4),20≦n₁≦120  (4),

(5) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₁ (cm) of the gas outlet satisfies the following formula (5),5≦D ₁ /d ₁₁≦30  (5), and

(6) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₂ (cm) of the liquid outlet satisfies the following formula(6),3≦D ₁ /d ₁₂≦20  (6);

(c) said second continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₂ (cm) and an inside diameter D₂ (cm),and having an internal with a number of stages n₂ thereinside, and has agas outlet having an inside diameter d₂₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₂₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7),

(2) said inside diameter D₂ (cm) of the column satisfies the followingformula (8),100≦D₂≦2000  (8),

(3) a ratio of the length L₂ (cm) to said inside diameter D₂ (cm) of thecolumn satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9),

(4) said number of stages n₂ satisfies the following formula (10),10≦n₂≦80  (10),

(5) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₁ (cm) of the gas outlet satisfies the following formula(11),2≦D ₂ /d ₂₁≦15  (11), and

(6) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₂ (cm) of the liquid outlet satisfies the following formula(12),5≦D ₂ /d ₂₂≦30  (12),

-   2. The process according to item 1, wherein distillation is carried    out simultaneously in said step (ii) and said step (iv),-   3. The process according to item 1 or 2, wherein an amount of said    diaryl carbonate produced is not less than 1 ton per hour.

In another aspect of the process according to the present invention,there is provided:

-   4. In a process for the production of an aromatic carbonate    containing a diaryl carbonate as a main product in which the    aromatic carbonate containing the diaryl carbonate as the main    product are produced continuously by taking a mixture of a dialkyl    carbonate and an aromatic monohydroxy compound as a starting    material, continuously feeding the starting material into a first    continuous multi-stage distillation column in which a catalyst is    present, carrying out the reaction and the distillation    simultaneously said the first column, continuously withdrawing a    first column low boiling point reaction mixture containing a    produced alcohol from an upper portion of said first column in a    gaseous form, continuously withdrawing a first column high boiling    point reaction mixture containing a produced alkyl aryl carbonate    from a lower portion of said first column in a liquid form,    continuously feeding the first column high boiling point reaction    mixture into a second continuous multi-stage distillation column in    which a catalyst is present, carrying out the reaction and the    distillation simultaneously in said second column, continuously    withdrawing a second column low boiling point reaction mixture    containing a produced dialkyl carbonate from an upper portion of    said second column in a gaseous form, continuously withdrawing a    second column high boiling point reaction mixture containing a    produced diaryl carbonate from a lower portion of said second column    in a liquid form while continuously feeding the second column low    boiling point reaction mixture containing the dialkyl carbonate into    the first continuous multi-stage distillation column, the    improvement in which:

(a) a molar ratio of the dialkyl carbonate to the aromatic monohydroxycompound in said starting material which is fed continuously into saidfirst continuous multi-stage distillation column is in a range of from0.1 to 10;

(b) said first continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₁ (cm) and an inside diameter D₁ (cm),and having an internal with a number of stages n₁ thereinside, and has agas outlet having an inside diameter d₁₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₁₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₁ (cm) satisfies the following formula (1),1500≦L₁≦8000  (1),

(2) said inside diameter D₁ (cm) of the column satisfies the followingformula (2),100≦D₁≦2000  (2),

(3) a ratio of said length L₁ (cm) to said inside diameter D₁ (cm) ofthe column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3),

(4) said number of stages n₁ satisfies the following formula (4),20≦n₁≦120  (4),

(5) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₁ (cm) of the gas outlet satisfies the following formula (5),5≦D ₁ /d ₁₁≦30  (5), and

(6) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₂ (cm) of the liquid outlet satisfies the following formula(6),3≦D ₁ /d ₁₂≦20  (6);

(c) said second continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₂ (cm) and an inside diameter D₂ (cm),and having an internal with a number of stages n₂ thereinside, and has agas outlet having an inside diameter d₂₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₂₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7),

(2) said inside diameter D₂ (cm) of the column satisfies the followingformula (8),100≦D₂≦2000  (8),

(3) a ratio of the length L₂ (cm) to said inside diameter D₂ (cm) of thecolumn satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9),

(4) said number of stages n₂ satisfies the following formula (10),10≦n₂≦80  (10),

(5) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₁ (cm) of the gas outlet satisfies the following formula(11),2≦D ₂ /d ₂₁≦15  (11), and

(6) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₂ (cm) of the liquid outlet satisfies the following formula(12),5≦D ₂ /d ₂₂≦30  (12),

-   5. The process according to item 4, wherein an amount produced of    the diaryl carbonate is not less than 1 ton per hour,-   6. The process according to any one of items 1 to 5, wherein d₁₁ and    d₁₂ satisfy the following formula (13), and d₂₁ and d₂₂ satisfy the    following formula (14)    1≦d ₁₂ /d ₁₁≦5  (13)    1≦d ₂₁ /d ₂₂≦6  (14),-   7. The process according to any one of items 1 to 6, wherein L₁, D₁,    L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for said first continuous multi-stage    distillation column satisfy the following formulae: 2000≦L₁≦6000,    150≦D₁≦1000, 3≦L₁/D₁≦30, 30≦n₁≦100, 8≦D₁/d₁₁≦25, and 5≦D₁/d₁₂≦18,    respectively, and

L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said second continuousmulti-stage distillation column satisfy the following formulae:2000≦L₂≦6000, 150≦D₂≦1000, 3≦L₂/D₂≦30, 15≦n₂≦60, 2.5≦D₂/d₂₁≦12, and7≦D₂/d₂₂≦25, respectively,

-   8. The process according to any one of items 1 to 7, wherein L₁, D₁,    L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for said first continuous multi-stage    distillation column satisfy the following formulae: 2500≦L₁≦5000,    200≦D₁≦800, 5≦L₁/D₁≦15, 40≦n₁≦90, 10≦D₁/d₁₁≦25, and 7≦D₁/d₁₂≦15,    respectively, and

L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said second continuousmulti-stage distillation column satisfy the following formulae:2500≦L₂≦5000, 200≦D₂≦800, 5≦L₂/D₂≦15, 20≦n₂≦50, 3≦D₂/d₂₁≦10, and9≦D₂/d₂₂≦20, respectively,

-   9. The process according to any one of items 1 to 8, wherein each of    said first continuous multi-stage distillation column and said    second continuous multi-stage distillation column is a distillation    column having a tray and/or a packing as the internal,-   10. The process according to item 9, wherein said first continuous    multi-stage distillation column is a plate-type distillation column    having the tray as the internal, and said second continuous    multi-stage distillation column is a distillation column having both    the packing and the tray as the internal,-   11. The process according to item 9 or 10, wherein each of the trays    in said first continuous multi-stage distillation column and said    second continuous multi-stage distillation column is a sieve tray    having a sieve portion and a down corner portion,-   12. The process according to item 11, wherein said sieve tray has    100 to 1000 holes/m² in the sieve portion,-   13. The process according to item 11 or 12, wherein the    cross-sectional area per hole of said sieve tray is in a range of    from 0.5 to 5 cm²,-   14. The process according to item 9 or 10, wherein said second    continuous multi-stage distillation column is a distillation column    having, as said internal, the packing in an upper portion of the    column, and the tray in a lower portion of the column,-   15. The process according to any one of items 9 to 14, wherein said    packing of said internal in said second continuous multi-stage    distillation column is one or more of a structured packing,-   16. The process according to item 15, wherein said structured    packing in said second continuous multi-stage distillation column is    of at least one selected from the group consisting of Mellapak,    Gempak, TECHNO-PAK, FLEXI-PAK, a Sulzer packing, a Goodroll packing    and a Glitchgrid,-   17. The process according to any one of items 1 to 16, wherein said    first continuous multi-stage distillation column comprises two or    more of distillation columns,-   18. The process according to any one of items 1 to 17, wherein said    second continuous multi-stage distillation column comprises two or    more of distillation columns.

In the second aspect of the present invention, there is provided:

-   19. An aromatic carbonate comprising a halogen content of not more    than 0.1 ppm, produced by the process according to any one of items    1 to 18.

In the third aspect of the present invention, there is provided:

-   20. A reactive distillation apparatus comprising a first continuous    multi-stage distillation column for carrying out reaction and    distillation; and a second continuous multi-stage distillation    column for carrying out reaction and distillation, which is    connected to said first continuous multi-stage distillation column,    comprising:

(a) said first continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₁ (cm) and an inside diameter D₁ (cm),and having an internal with a number of stages n₁ thereinside, and has agas outlet having an inside diameter d₁₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₁₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₁ (cm) satisfies the following formula (1),1500≦L₁≦8000  (1),

(2) said inside diameter D₁ (cm) of the column satisfies the followingformula (2),100≦D₁≦2000  (2),

(3) a ratio of said length L₁ (cm) to said inside diameter D₁ (cm) ofthe column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3),

(4) said number of stages n₁ satisfies the following formula (4),20≦n₁≦120  (4),

(5) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₁ (cm) of the gas outlet satisfies the following formula (5),5≦D ₁ /d ₁₁≦30  (5), and

(6) a ratio of said inside diameter D₁ (cm) of the column to said insidediameter d₁₂ (cm) of the liquid outlet satisfies the following formula(6),3≦D ₁ /d ₁₂≦20  (6);

(b) said second continuous multi-stage distillation column comprises astructure having a pair of end plates above and below a cylindricaltrunk portion having a length L₂ (cm) and an inside diameter D₂ (cm),and having an internal with a number of stages n₂ thereinside, and has agas outlet having an inside diameter d₂₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₂₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein

(1) said length L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7),

(2) said inside diameter D₂ (cm) of the column satisfies the followingformula (8),100≦D₂≦2000  (8),

(3) a ratio of the length L₂ (cm) to said inside diameter D₂ (cm) of thecolumn satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9)

(4) said number of stages n₂ satisfies the following formula (10),10≦n₂≦80  (10),

(5) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₁ (cm) of the gas outlet satisfies the following formula(11),2≦D ₂ /d ₂₁≦15  (11), and

(6) a ratio of said inside diameter D₂ (cm) of the column to said insidediameter d₂₂ (cm) of the liquid outlet satisfies the following formula(12),5≦D ₂ /d ₂₂≦30  (12),

-   21. The reactive distillation apparatus according to item 20,    wherein d₁₁ and d₁₂ satisfy the following formula (13), and d₂₁ and    d₂₂ satisfy the following formula (14)    1≦d ₁₂ /d ₁₁≦5  (13)    1≦d ₂₁ /d ₂₂≦6  (14),-   22. The reactive distillation apparatus according to item 20 or 21,    wherein L₁, D₁, L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for said first    continuous multi-stage distillation column satisfy the following    formulae: 2000≦L₁≦6000, 150≦D₁≦1000, 3≦L₁/D₁≦30, 30≦n₁≦100,    8≦D₁/d₁₁≦25, and 5≦D₁/d₁₂≦18, respectively, and

L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said second continuousmulti-stage distillation column satisfy the following formulae:2000≦L₂≦6000, 150≦D₂≦1000, 3≦L₂/D₂≦30, 15≦n₂≦60, 2.5≦D₂/d₂₁≦12, and7≦D₂/d₂₂≦25, respectively,

-   23. The reactive distillation apparatus according to any one of    items 20 to 22, wherein L₁, D₁, L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for    said first continuous multi-stage distillation column satisfy the    following formulae: 2500≦L₁≦5000, 200≦D₁≦800, 5≦L₁/D₁≦15, 40≦n₁≦90,    10≦D₁/d₁₁≦25, and 7≦D₁/d₁₂≦15, respectively, and

L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said second continuousmulti-stage distillation column satisfy the following formulae:2500≦L₂≦5000, 200≦D₂≦800, 5≦L₂/D₂≦15, 20≦n₂≦50, 3≦D₂/d₂₁≦10, and9≦D₂/d₂₂≦20, respectively,

-   24. The reactive distillation apparatus according to any one of    items 20 to 23, wherein each of said first continuous multi-stage    distillation column and said second continuous multi-stage    distillation column is a distillation column having a tray and/or a    packing as the internal,-   25. The reactive distillation apparatus according to item 24,    wherein said first continuous multi-stage distillation column is a    plate-type distillation column having the tray as the internal, and    said second continuous multi-stage distillation column is a    distillation column having both the packing and the tray as the    internal,-   26. The reactive distillation apparatus according to item 24 or 25,    wherein each of the trays in said first continuous multi-stage    distillation column and said second continuous multi-stage    distillation column is a sieve tray having a sieve portion and a    down corner portion,-   27. The reactive distillation apparatus according to item 26,    wherein said sieve tray has 100 to 1000 holes/m² in the sieve    portion,-   28. The reactive distillation apparatus according to item 26 or 27,    wherein the cross-sectional area per hole of said sieve tray is in a    range of from 0.5 to 5 cm²,-   29. The process according to item 24 or 25, wherein said second    continuous multi-stage distillation column is a distillation column    having, as said internal, the packing in an upper portion of the    column, and the tray in a lower portion of the column,-   30. The reactive distillation apparatus according to any one of    items 24 to 29, wherein said packing of said internal in said second    continuous multi-stage distillation column is one or more of a    structured packing,-   31. The reactive distillation apparatus according to item 30,    wherein said structured packing in said second continuous    multi-stage distillation column is of at least one selected from the    group consisting of Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, a    Sulzer packing, a Goodroll packing and a Glitchgrid,-   32. The reactive distillation apparatus according to any one of    items 20 to 31, wherein said first continuous multi-stage    distillation column comprises two or more of distillation columns,-   33. The reactive distillation apparatus according to any one of    items 20 to 32, wherein said second continuous multi-stage    distillation column comprises two or more of distillation columns.

ADVANTAGEOUS EFFECTS OF THE INVENTION

It has been discovered that according to the present invention, from adialkyl carbonate and an aromatic monohydroxy compound, an aromaticcarbonate containing a diaryl carbonate as a main product can beproduced on an industrial scale of not less than 1 ton per hour,preferably not less than 2 tons per hour, more preferably not less than3 tons per hour, with a high selectivity of not less than 95%,preferably not less than 97%, more preferably not less than 99%, stablyfor a prolonged period of time of not less than 2000 hours, preferablynot less than 3000 hours, more preferably not less than 5000 hours. Adiaryl carbonate obtained by subjecting the aromatic carbonatescontaining the diaryl carbonate as a main component obtained through thepresent invention to separation/purification through distillation or thelike is of high purity, and is useful as a raw material of atransesterification method polycarbonate or polyester carbonate or thelike, or as a raw material of a non-phosgene method isocyanate orurethane or the like. Moreover, according to the present invention,because a starting material and catalyst not containing a halogen aregenerally used, the diaryl carbonate obtained has a halogen content ofnot more than 0.1 ppm, preferably not more than 10 ppb, more preferablynot more than 1 ppb.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic view of a first continuous multi-stagedistillation column for carrying out the present invention, thedistillation column having an internal provided inside a trunk portionthereof;

FIG. 2 is a schematic view of a second continuous multi-stagedistillation column preferable for carrying out the present invention,the distillation column having, provided inside a trunk portion thereof,an internal comprising a structured packing (6-1) in an upper portionand a sieve tray (6-2) in a lower portion; and

FIG. 3 is a schematic view of an apparatus suitable for carrying out thepresent invention.

DESCRIPTION OF REFERENCE NUMERALS

1: gas outlet, 2: liquid outlet, 3, 4, 15, 19, 25, 29: inlet, 5: endplate, 6: internal, 6-1: internal (packing), 6-2: internal (tray), 7:trunk portion, L₁, L₂: length of trunk portion (cm), D₁, D₂: insidediameter of trunk portion (cm), d₁₁, d₂₁: inside diameter of gas outlet(cm), d₁₂, d₂₂: inside diameter of liquid outlet (cm), 101: the firstmulti-stage distillation column, 201: the second multi-stagedistillation column, 11, 12, 21: inlet, 13, 23; a column top gas outlet,14, 24, 18, 28: heat exchanger, 15, 25: reflux liquid inlet, 16, 26: acolumn top component outlet, 17, 27: a column bottom liquid outlet, 31:a column bottom component outlet of the second multi-stage distillationcolumn.

BEST MODE FOR CARRYING OUT THE INVENTION

In the following, the present invention is described in detail.

A dialkyl carbonate used in the present invention is a compoundrepresented by the following formula (15).R¹OCOOR¹  (15)wherein R¹ represents an alkyl group having 1 to 10 carbon atoms, analicyclic group having 3 to 10 carbon atoms, or an aralkyl group having6 to 10 carbon atoms. Examples of R¹ include alkyl groups such asmethyl, ethyl, propyl (isomers), allyl, butyl (isomers), butenyl(isomers), pentyl (isomers), hexyl (isomers), heptyl (isomers), octyl(isomers), nonyl (isomers), decyl (isomers) and cyclohexylmethyl;alicyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl; and aralkyl groups such as benzyl, phenethyl(isomers), phenylpropyl (isomers), phenylbutyl (isomers) andmethylbenzyl (isomers). The above-mentioned alkyl groups, alicyclicgroups and aralkyl groups may be substituted with other substitutentssuch as a lower alkyl group, a lower alkoxy group, a cyano group or ahalogen atom, and may also contain an unsaturated bond.

Examples of dialkyl carbonates having such R¹ include dimethylcarbonate, diethyl carbonate, dipropyl carbonate (isomers), diallylcarbonate, dibutenyl carbonate (isomers), dibutyl carbonate (isomers),dipentyl carbonate (isomers), dihexyl carbonate (isomers), diheptylcarbonate (isomers), dioctyl carbonate (isomers), dinonyl carbonate(isomers), didecyl carbonate (isomers), dicyclopentyl carbonate,dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate,diphenethyl carbonate (isomers), di(phenylpropyl)carbonate (isomers),di(phenylbutyl)carbonate (isomers), di(chlorobenzyl)carbonate (isomers),di(methoxybenzyl)carbonate (isomers), di(methoxymethyl)carbonate,di(methoxyethyl)carbonate (isomers), di(chloroethyl)carbonate (isomers)and di(cyanoethyl)carbonate (isomers).

Of these dialkyl carbonates, ones preferably used in the presentinvention are dialkyl carbonates in which R¹ is an alkyl group havingnot more than four carbon atoms and not containing a halogen atom. Aparticularly preferable one is dimethyl carbonate. Moreover, ofpreferable dialkyl carbonates, particularly preferable ones are dialkylcarbonates produced in a state substantially not containing a halogenatom, for example, ones produced from an alkylene carbonatesubstantially not containing a halogen atom and an alcohol substantiallynot containing a halogen atom.

An aromatic monohydroxy compound used in the present invention is acompound represented by the following formula (16). The type of thearomatic monohydroxy compound is not limited, so long as the hydroxylgroup is directly bonded to the aromatic group;Ar¹OH  (16)wherein Ar¹ represents an aromatic group having 5 to 30 carbon atoms.Examples of aromatic monohydroxy compounds having such Ar¹ includephenol; various alkylphenols such as cresol (isomers), xylenol(isomers), trimethylphenol (isomers), tetramethylphenol (isomers),ethylphenol (isomers), propylphenol (isomers), butylphenol (isomers),diethylphenol (isomers), methylethylphenol (isomers), methylpropylphenol(isomers), dipropylphenol (isomers), methylbutylphenol (isomers),pentylphenol (isomers), hexylphenol (isomers) and cyclohexylphenol(isomers); various alkoxyphenols such as methoxyphenol (isomers) andethoxyphenol (isomers); arylalkylphenols such as phenylpropylphenol(isomers); naphthol (isomers) and various substituted naphthols; andheteroaromatic monohydroxy compounds such as hydroxypyridine (isomers),hydroxycoumarin (isomers) and hydroxyquinoline (isomers).

Of these aromatic monohydroxy compounds, ones preferably used in thepresent invention are aromatic monohydroxy compounds in which Ar¹ is anaromatic group having 6 to 10 carbon atoms. Phenol is particularlypreferable. Moreover, of these aromatic monohydroxy compounds, onessubstantially not containing a halogen are preferably used in thepresent invention.

The molar ratio of the dialkyl carbonate to the aromatic monohydroxycompound used as the starting material of the present invention must bein a range of from 0.1 to 10. Outside this range, an amount of unreactedmaterial remaining, based on a prescribed amount of the alkyl arylcarbonate produced becomes high, which is not efficient for theproduction of the aromatic carbonate. Moreover, much energy is requiredto recover the alkyl aryl carbonate. For such reasons, the above molarratio is preferably in a range of from 0.5 to 5.0, more preferably 0.8to 3.0, yet more preferably from 1.0 to 2.0.

In the present invention, not less than 1 ton per hour of the diarylcarbonate is produced continuously. The minimum amount of the aromaticmonohydroxy compound fed in continuously for the above production isgenerally 15 P ton/hr, preferably 13 P ton/hr, more preferably 10 Pton/hr, based on the amount of the aromatic carbonate (P ton/hr) to beproduced. More preferably, this amount can be made to be less than 8.0 Pton/hr.

The dialkyl carbonate and the aromatic monohydroxy compound used as thestarting material of the present invention may be of high purity, or maycontain other compounds, for example may contain compounds or reactionby-products produced in the first continuous multi-stage distillationcolumn and/or the second continuous multi-stage distillation column. Inthe case of industrial implementation, for the starting material,besides fresh dialkyl carbonate and aromatic monohydroxy compound newlyintroduced into the reaction system, it is also preferable to use thedialkyl carbonate and the aromatic monohydroxy compound recovered fromthe first continuous multi-stage distillation column and/or the secondcontinuous multi-stage distillation column. In the process of thepresent invention, the column top component that contains a low boilingpoint reaction mixture in the second continuous multi-stage distillationcolumn are fed into the first continuous multi-stage distillationcolumn. In this case, the second column low boiling point reactionmixture may be fed into the first continuous multi-stage distillationcolumn as is, or after some of the components thereof have beenseparated out. Accordingly, in the present invention, which isimplemented industrially, it is preferable for the starting material fedinto the first continuous multi-stage distillation column to contain analcohol, an alkyl aryl carbonate, a diaryl carbonate, an alkyl arylether, and so on. A starting material further containing small amountsof high boiling point by-products such as Fries rearrangement productsof the alkyl aryl carbonate and diaryl carbonate which are the products,derivatives thereof, and so on can also be preferably used. In thepresent invention, for example, when producing methyl phenyl carbonateand diphenyl carbonate using as the starting material a mixture ofdimethyl carbonate as the dialkyl carbonate and phenol as the aromaticmonohydroxy compound, it is preferable for this starting material tocontain methyl alcohol, and methyl phenyl carbonate and diphenylcarbonate, which are the reaction products, and the starting materialmay further contain small amounts of anisole, phenyl salicylate andmethyl salicylate, which are reaction by-products, and high boilingpoint by-products derived therefrom.

The aromatic carbonates produced in the present invention refer to analkyl aryl carbonate, a diaryl carbonate, or a mixture thereof,obtainable through the transesterification reaction between the dialkylcarbonate and the aromatic monohydroxy compound. Included under thistransesterification reaction are a reaction in which one or two of thealkoxy groups of the dialkyl carbonate is/are exchanged with an aryloxygroup of the aromatic monohydroxy compound so as to eliminate analcohol, and a reaction in which two molecules of the alkyl arylcarbonate produced are converted into the diaryl carbonate and thedialkyl carbonate through a transesterification reaction therebetween,i.e. a disproportionation reaction. In the present invention, in thefirst continuous multi-stage distillation column, the alkyl arylcarbonate is mainly obtained, and in the second continuous multi-stagedistillation column, the aromatic carbonates containing the diarylcarbonate as a main product are mainly obtainable through thedisproportionation reaction of the alkyl aryl carbonate. In the presentinvention, it is particularly preferable for a starting material andcatalyst not containing a halogen to be used; in this case, the diarylcarbonate produced does not contain a halogen at all, and hence it isimportant as a raw material when industrially producing a polycarbonateby means of the transesterification method. The reason for this is thatif a halogen is present in the raw material for the polymerization evenin a small amount of less than 1 ppm, then this may inhibit thepolymerization reaction, or cause a deterioration of the properties of,or discoloration of, the polycarbonate produced.

As a catalyst used in the first continuous multi-stage distillationcolumn and/or the second continuous multi-stage distillation columnaccording to the present invention, for example, a metal-containingcompound selected from the following compounds can be used:

<Lead Compounds>

Lead oxides such as PbO, PbO₂ and Pb₃O₄; lead sulfides such as PbS andPb₂S; lead hydroxides such as Pb(OH)₂ and Pb₂O₂(OH)₂; plumbites such asNa₂PbO₂, K₂PbO₂, NaHPbO₂ and KHPbO₂; plumbates such as Na₂PbO₃,Na₂H₂PbO₄, K₂PbO₃, K₂[Pb(OH)₆], K₄PbO₄, Ca₂PbO₄ and CaPbO₃; leadcarbonates and basic salts thereof such as PbCO₃ and 2PbCO₃.Pb(OH)₂;lead salts of organic acids, and carbonates and basic salts thereof,such as Pb(OCOCH₃)₂, Pb(OCOCH₃)₄ and Pb(OCOCH₃)₂.PbO.3H₂O, organoleadcompounds such as Bu₄Pb, Ph₄Pb, Bu₃PbCl, Ph₃PbBr, Ph₃Pb (or Ph₆Pb₂),Bu₃PbOH and Ph₃PbO (wherein Bu represents a butyl group, and Phrepresents a phenyl group); alkoxylead compounds and aryloxyleadcompounds such as Pb(OCH₃)₂, (CH₃O)Pb(OPh) and Pb(OPh)₂; lead alloyssuch as Pb—Na, Pb—Ca, Pb—Ba, Pb—Sn and Pb—Sb; lead minerals such asgalena and zinc blende; and hydrates of such lead compounds;

<Copper Family Metal Compounds>

Salts and complexes of copper family metals such as CuCl, CuCl₂, CuBr,CuBr₂, CuI, CuI₂, Cu(OAc)₂, Cu(acac)₂, copper oleate, Bu₂Cu, (CH₃O)₂Cu,AgNO₃, AgBr, silver picrate, AgC₆H₆ClO₄, [AuC≡C—C(CH₃)₃]_(n) and[Cu(C₇H₈)Cl]₄ (wherein acac represents an acetylacetone chelate ligand);

<Alkali Metal Complexes>

Alkali metal complexes such as Li(acac) and LiN(C₄H₉)₂;

<Zinc Complexes>

Zinc complexes such as Zn(acac)₂;

<Cadmium Complexes>

Cadmium complexes such as Cd(acac)₂;

<Iron Family Metal Compounds>

Complexes of iron family metals such as Fe(C₁₀H₈)(CO)₅, Fe(CO)₅,Fe(C₄H₆)(CO)₃, Co(mesitylene)₂, (PEt₂Ph)₂, CoC₅F₅(CO)₇, Ni-π-C₅H₅NO andferrocene;

<Zirconium Complexes>

Zirconium complexes such as Zr(acac)₄ and zirconocene;

<Lewis Acid Type Compounds>

Lewis acids and Lewis acid-forming transition metal compounds such asAlX₃, TiX₃, TiX₄, VOX₃, VX₅, ZnX₂, FeX₃ and SnX₄ (wherein X represents ahalogen atom, an acetoxy group, an alkoxy group or an aryloxy group);and

<Organo-Tin Compounds>

Organo-tin compounds such as (CH₃)₃SnOCOCH₃, (C₂H₅)₃SnOCOC₆H₅,Bu₃SnOCOCH₃, Ph₃SnOCOCH₃, Bu₂Sn(OCOCH₃)₂, Bu₂Sn(OCOC₁₁H₂₃)₂, Ph₃SnOCH₃,(C₂H₅)₃SnOPh, Bu₂Sn(OCH₃)₂, Bu₂Sn(OC₂H₅)₂, Bu₂Sn(OPh)₂, Ph₂Sn(OCH₃)₂,(C₂H₅)₃SnOH, Ph₃SnOH, Bu₂SnO, (C₈H₁₇)₂SnO, Bu₂SnCl₂ and BuSnO(OH).

Each of these catalysts may be a solid catalyst fixed inside themulti-stage distillation column, or may be a soluble catalyst thatdissolves in the reaction system.

Each of these catalyst components may of course have been reacted withan organic compound present in the reaction system such as an aliphaticalcohol, the aromatic monohydroxy compound, the alkyl aryl carbonate,the diaryl carbonate or the dialkyl carbonate, or may have beensubjected to heating treatment with the starting material or productsprior to the reaction.

In the case of carrying out the present invention with a solublecatalyst that dissolves in the reaction system, the catalyst ispreferably one having a high solubility in the reaction liquid under thereaction conditions. Examples of preferable catalysts in this senseinclude PbO, Pb(OH)₂ and Pb(OPh)₂; TiCl₄, Ti(OMe)₄, (MeO)Ti(OPh)₃,(MeO)₂Ti(OPh)₂, (MeO)₃Ti(OPh) and Ti(OPh)₄; SnCl₄, Sn(OPh)₄, Bu₂SnO andBu₂Sn(OPh)₂; FeCl₃, Fe(OH)₃ and Fe(OPh)₃; and such catalysts that havebeen treated with phenol, the reaction liquid or the like.

FIG. 1 shows a schematic view of the first continuous multi-stagedistillation column for carrying out a production process according tothe present invention. The continuous multi-stage distillation column101 used in the present invention comprises a structure having a pair ofend plates 5 above and below a cylindrical trunk portion 7 having alength L₁ (cm) and an inside diameter D₁ (cm), and having an internal 6with a number of stages n thereinside, and has a gas outlet 1 having aninside diameter d₁₁ (cm) at the top of the column or in an upper portionof the column near to the top, a liquid outlet 2 having an insidediameter d₁₂ (cm) at the bottom of the column or in a lower portion ofthe column near to the bottom, at least one inlet 3 provided in theupper portion and/or a middle portion of the column below the gasoutlet, and at least one inlet 4 provided in the lower portion of thecolumn above the liquid outlet.

More specifically, the following are required for the first continuousmulti-stage distillation column 101 according to the present invention:

(1) the length L₁ (cm) must satisfy formula (1),1500≦L₁≦8000  (1),

(2) the inside diameter D1 (cm) of the column must satisfy formula (2),100≦D₁≦2000  (2),

(3) a ratio of the length L₁ (cm) to the inside diameter D₁ (cm) of thecolumn must satisfy formula (3),2≦L ₁ /D ₁≦40  (3),

(4) the number of stages n₁ must satisfy formula (4),20≦n₁≦120  (4),

(5) a ratio of the inside diameter D₁ (cm) of the column to the insidediameter d₁₁ (cm) of the gas outlet must satisfy formula (5),5≦D ₁ /d ₁₁≦30  (5), and

(6) a ratio of the inside diameter D₁ (cm) of the column to the insidediameter d₁₂ (cm) of the liquid outlet must satisfy formula (6),3≦D ₁ /d ₁₂≦20  (6).

FIG. 2 shows a schematic view of the second continuous multi-stagedistillation column for carrying out a production process according tothe present invention. The second continuous multi-stage distillationcolumn 201 used in the present invention comprises a structure having apair of end plates 5 above and below a cylindrical trunk portion 7having a length L₂ (cm) and an inside diameter D₂ (cm), and having aninternal (6-1: packing, 6-2: tray) with a number of stages n₂thereinside, and has a gas outlet 1 having an inside diameter d₂₁ (cm)at the top of the column or in an upper portion of the column near tothe top, a liquid outlet 2 having an inside diameter d₂₂ (cm) at thebottom of the column or in a lower portion of the column near to thebottom, at least one inlet 3 provided in the upper portion and/or amiddle portion of the column below the gas outlet, and at least oneinlet 4 provided in the lower portion of the column above the liquidoutlet.

More specifically, the following are required for the second continuousmulti-stage distillation column 201 according to the present invention:

(1) the length L₂ (cm) must satisfy formula (7),1500≦L₂≦8000  (7),

(2) the inside diameter D₂ (cm) of the column must satisfy formula (8),100≦D₂≦2000  (8),

(3) a ratio of the length L₂ (cm) to the inside diameter D₂ (cm) of thecolumn must satisfy formula (9),2≦L ₂ /D ₂≦40  (9),

(4) the number of stages n₂ must satisfy formula (10),10≦n₂≦80  (10),

(5) a ratio of the inside diameter D₂ (cm) of the column to the insidediameter d₂₁ (cm) of the gas outlet must satisfy formula (11),2≦D ₂ /d ₂₁≦15  (11), and

(6) a ratio of the inside diameter D₂ (cm) of the column to the insidediameter d₂₂ (cm) of the liquid outlet must satisfy formula (12),5≦D ₂ /d ₂₂≦30  (12).

Note that since FIGS. 1 and 2 show embodiments of the continuousmulti-stage distillation columns according to the present invention,arrangement of the internal is not limited to that of FIGS. 1 and 2. Itshould be noted that the term “in an upper portion of the column near tothe top” refers to the portion extending downwardly from the top of thecolumn to the location measuring about 0.25 L₁ or 0.25 L₂, and the term“in a lower portion of the column near to the bottom” refers to theportion extending upwardly from the bottom of the column to the locationmeasuring about 0.25L₁ or 0.25L₂. Note that L₁ and L2 are defined above.

It has been discovered that by using the first continuous multi-stagedistillation column and the second continuous multi-stage distillationcolumn that simultaneously satisfy formulae (1) to (12), aromaticcarbonates containing a diaryl carbonate as a main product can beproduced from a dialkyl carbonate and an aromatic monohydroxy compoundon an industrial scale of not less than 1 ton per hour with highselectivity and high productivity stably for a prolonged period of time,for example not less than 2000 hours, preferably not less than 3000hours, more preferably not less than 5000 hours. The reason why it hasbecome possible to produce aromatic carbonates on an industrial scalewith such excellent effects by implementing the process of the presentinvention is not clear, but this is supposed to be due to a combinedeffect brought about when the conditions of formulae (1) to (12) arecombined. Preferable ranges for the respective factors are describedbelow.

If each of L₁ (cm) and L₂ (cm) is less than 1500, then the conversiondecreases and hence it is not possible to attain the desired productionamount. Moreover, to keep down the equipment cost while securing theconversion enabling the desired production amount to be attained, eachof L₁ and L₂ must be made to be not more than 8000. More preferableranges for L₁ (cm) and L₂ (cm) are 2000≦L₁≦6000 and 2000≦L₂≦6000,respectively with 2500≦L₁≦5000 and 2500≦L₂≦5000 being yet morepreferable.

If each of D₁ (cm) and D₂ (cm) is less than 100, then it is not possibleto attain the desired production amount. Moreover, to keep down theequipment cost while attaining the desired production amount, each of D₁and D₂ must be made to be not more than 2000. More preferable ranges forD₁ (cm) and D₂ (cm) are 150≦D₁≦1000 and 150≦D₂≦1000, respectively with200≦D₁≦800 and 200≦D₂≦800 being yet more preferable. For the firstcontinuous multi-stage distillation column and the second continuousmulti-stage distillation column, so long as D₁ and D₂ are within theabove ranges, each of the columns may have the same inside diameter fromthe upper portion thereof to the lower portion thereof, or the insidediameter may differ from different portions. For example, for each ofthe continuous multi-stage distillation columns, the inside diameter ofthe upper portion of the column may be smaller than, or larger than, theinside diameter of the lower portion of the column.

If each of L₁/D₁ and L₂/D₂ is less than 2 or greater than 40, thenstable operation becomes difficult. In particular, if L₁/D₁ or L₂/D₂ isgreater than 40, then the pressure difference between the top and bottomof the column becomes too great, and hence prolonged stable operationbecomes difficult. Moreover, it becomes necessary to increase thetemperature in the lower portion of the column, and hence side reactionsbecome liable to occur, bringing about a decrease in the selectivity.More preferable ranges for L₁/D₁ and L₂/D₂ are 3≦L₁/D₁≦30 and3≦L₂/D₂≦30, respectively with 5≦L₁/D₁≦15 and 5≦L₂/D₂≦15 being yet morepreferable.

If n₁ is less than 20, then the conversion decreases and it is notpossible to attain the desired production amount for the firstcontinuous multi-stage distillation column. Moreover, to keep down theequipment cost while securing the conversion enabling the desiredproduction amount to be attained, n₁ must be made to be not more than120. Furthermore, if n₁ is greater than 120, then the pressuredifference between the top and bottom of the column becomes too great,and hence prolonged stable operation of the first continuous multi-stagedistillation column becomes difficult. Moreover, it becomes necessary toincrease the temperature in the lower portion of the column, and henceside reactions become liable to occur, bringing about a decrease in theselectivity. A more preferable range for n₁ is 30≦n₁≦100, with 40≦n₁≦90being yet more preferable. Moreover, if n₂ is less than 10, then theconversion decreases and it is not possible to attain the desiredproduction amount for the second continuous multi-stage distillationcolumn. Moreover, to keep down the equipment cost while securing theconversion enabling the desired production amount to be attained, n₂must be made to be not more than 80. Furthermore, if n₂ is greater than80, then the pressure difference between the top and bottom of thecolumn becomes too great, and hence prolonged stable operation of thesecond continuous multi-stage distillation column becomes difficult.Moreover, it becomes necessary to increase the temperature in the lowerportion of the column, and hence side reactions become liable to occur,bringing about a decrease in the selectivity. A more preferable rangefor n₂ is 15≦n₂≦60, with 20≦n₂≦50 being yet more preferable.

If D₁/d₁₁ is less than 5, then the equipment cost for the firstcontinuous multi-stage distillation column becomes high. Moreover, largeamounts of gaseous components are readily released to the outside of thesystem, and hence stable operation of the first continuous multi-stagedistillation column becomes difficult. If D₁/d₁₁ is greater than 30,then the gaseous component withdrawal amount becomes relatively low, andhence stable operation becomes difficult, and moreover a decrease in theconversion is brought about. A more preferable range for D₁/d₁₁ is8≦D₁/d₁₁≦25, with 10≦D₁/d₁₁≦20 being yet more preferable. Furthermore,if D₂/d₂₁ is less than 2, then the equipment cost for the secondcontinuous multi-stage distillation column becomes high. Moreover, largeamounts of gaseous components are readily released to the outside of thesystem, and hence stable operation of the second continuous multi-stagedistillation column becomes difficult. If D₂/d₂₁ is greater than 15,then the gaseous component withdrawal amount becomes relatively low, andhence stable operation becomes difficult, and moreover a decrease in theconversion is brought about. A more preferable range for D₂/d₂₁ is5≦D₂/d₂₁≦12, with 3≦D₂/d₂₁≦10 being yet more preferable.

If D₁/d₁₂ is less than 3, then the equipment cost for the firstcontinuous multi-stage distillation column becomes high. Moreover, theliquid withdrawal amount becomes relatively high, and hence stableoperation of the first continuous multi-stage distillation columnbecomes difficult. If D₁/d₁₂ is greater than 20, then the flow ratethrough the liquid outlet and piping becomes excessively fast, and henceerosion becomes liable to occur, bringing about corrosion of theapparatus. A more preferable range for D₁/d₁₂ is 5≦D₁/d₁₂≦18, with7≦D₁/d₁₂≦15 being yet more preferable. Furthermore, if D₂/d₂₂ is lessthan 5, then the equipment cost for the second continuous multi-stagedistillation column becomes high. Moreover, the liquid withdrawal amountbecomes relatively high, and hence stable operation of the secondcontinuous multi-stage distillation column becomes difficult. If D₂/d₂₂is greater than 30, then the flow rate through the liquid outlet andpiping becomes excessively fast, and hence erosion becomes liable tooccur, bringing about corrosion of the apparatus. Amore preferable rangefor D₂/d₂₂ is 7≦D₂/d₂₂≦25, with 9≦D₂/d₂₂≦20 being yet more preferable.

Furthermore, it has been found that in the present invention it isfurther preferable for d₁₁ and d₁₂ to satisfy the formula (13), and ford₂₁ and d₂₂ to satisfy the formula (14).1≦d ₁₂ /d ₁₁≦5  (13)1≦d ₂₁ /d ₂₂≦6  (14).

The term “prolonged stable operation” used in the present inventionmeans that operation can be carried out continuously in a steady statebased on the operating conditions with no clogging of piping or erosionfor not less than 1000 hours, preferably not less than 3000 hours, morepreferably not less than 5000 hours, and a prescribed amount of thearomatic carbonates containing the diaryl carbonate as a main productcan be produced while maintaining high selectivity.

A characteristic feature of the present invention is that the aromaticcarbonates can be produced stably for a prolonged period of time withhigh selectivity and with a high productivity of not less than 1 ton perhour, preferably not less than 2 tons per hour, more preferably not lessthan 3 tons per hour. Moreover, another characteristic feature of thepresent invention is that in the case that L₁, D₁, L₁/D₁, n₁, D₁/d₁₁,and D₁/d₁₂ for the first continuous multi-stage distillation columnsatisfy the following formulae: 2000≦L₁≦6000, 150≦D₁≦1000, 3≦L₁/D₁≦30,30≦n₁≦100, 8≦D₁/d₁₁≦25, and 5≦D₁/d₁₂≦18, respectively, and L₂, D₂,L₂/D₂, n₂, D₂/d₂₁ and D₂/d₂₂ for the second continuous multi-stagedistillation column satisfy the following formulae: 2000≦L₂≦6000,150≦D₂≦1000, 3≦L₂/D₂≦30, 15≦n₂≦60, 2.5≦D₂/d₂₁≦12, and 7≦D₂/d₂₂≦25,respectively, not less than 2 tons per hour, preferably not less than2.5 tons per hour, more preferably not less than 3 tons per hour of thearomatic carbonates can be produced. Furthermore, another characteristicfeature of the present invention is that in the case that L₁, D₁, L₁/D₁,n₁, D₁/d₁₁, and D₁/d₁₂ for the first continuous multi-stage distillationcolumn satisfy the following formulae: 2500≦L₁≦5000, 200≦D₁≦800,5≦L₁/D₁≦15, 40≦n₁≦90, 10≦D₁/d₁₁≦25, and 7≦D₁/d₁₂≦15, respectively andL₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for the second continuousmulti-stage distillation column satisfy the following formulae:2500≦L₂≦5000, 200≦D₂≦800, 5≦L₂/D₂≦10, 20≦n₂≦50, 3≦D₂/d₂₁≦10, and9≦D₂/d₂₂≦20, respectively, not less than 3 tons per hour, preferably notless than 3.5 tons per hour, more preferably not less than 4 tons perhour of the aromatic carbonates can be produced.

“Selectivity for the aromatic carbonates” in the present invention isbased on the aromatic monohydroxy compound reacted. In the presentinvention, a high selectivity of not less than 95% can generally beattained, preferably not less than 97%, more preferably not less than98%.

Each of the first continuous multi-stage distillation column and thesecond continuous multi-stage distillation column used in the presentinvention is preferably a distillation column having a tray and/or apacking as the internal. The term “internal” used in the presentinvention means the parts in the distillation column where gas andliquid are actually brought into contact with one another. As the tray,for example, a bubble-cap tray, a sieve tray, a valve tray, acounterflow tray, a Superfrac tray, a Maxfrac tray, or the like arepreferable. As the packing, a random packing such as a Raschig ring, aLessing ring, a Pall ring, a Berl saddle, an Intalox saddle, a Dixonpacking, a McMahon packing or a Heli-Pak, or a structured packing suchas Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, a Sulzer packing, a Goodrollpacking or a Glitchgrid are preferable. The multi-stage distillationcolumn having both a tray portion and a portion packed with the packingcan also be used. Note that the term “number of stages (n) of aninternal” used in the present invention means that the total number oftrays in the case of a tray, and the theoretical number of stages in thecase of a packing. Therefore, in the case of the multi-stage columnhaving both the tray portion and the portion packed with the packing, nmeans the sum of the total number of trays and the theoretical number ofstages of the packing.

In the first continuous multi-stage distillation column of the presentinvention, a reaction in which the alkyl aryl carbonate is produced fromthe dialkyl carbonate and the aromatic monohydroxy compound mainlyoccurs. This reaction has an extremely low equilibrium constant, and thereaction rate is slow, and hence it has been discovered that aplate-type distillation column having the tray as the internal isparticularly preferable as the first continuous multi-stage distillationcolumn used in the reactive distillation. Moreover, in the secondcontinuous multi-stage distillation column, it is mainly adisproportionation reaction of the alkyl aryl carbonate that occurs.This reaction also has a low equilibrium constant, and a slow reactionrate. It has been discovered that a distillation column having both thepacking and the tray as the internal is preferable as the secondcontinuous multi-stage distillation column used in the reactivedistillation. Furthermore, it has been discovered that a distillationcolumn having the packing installed in the upper portion thereof and thetray installed in the lower portion thereof is preferable as the secondcontinuous multi-stage distillation column. It has been discovered thatthe packing in the second continuous multi-stage distillation column ispreferably structured packing. Of the structured packing, Mellapak isparticularly preferable.

Furthermore, it has been discovered that, as each of the tray installedin the first continuous multi-stage distillation column and the secondcontinuous multi-stage distillation column, a sieve tray having a sieveportion and a down corner portion is particularly good in terms of therelationship between performance and equipment cost. It has also beendiscovered that the sieve tray preferably has 100 to 1000 holes/m² inthe sieve portion. A more preferable number of holes is 120 to 900holes/m², yet more preferably 150 to 800 holes/m². Moreover, it has beendiscovered that the cross-sectional area per hole of the sieve tray ispreferably in a range of from 0.5 to 5 cm². A more preferablecross-sectional area per hole is 0.7 to 4 cm², yet more preferably 0.9to 3 cm². Furthermore, it has been discovered that it is particularlypreferable if the sieve tray has 100 to 1000 holes/m² in the sieveportion and the cross-sectional area per hole is in a range of from 0.5to 5 cm². It has been shown that by adding the above conditions to thecontinuous multi-stage distillation columns, the object of the presentinvention can be attained more easily.

When carrying out the present invention, aromatic carbonates containinga diaryl carbonate as a main product are continuously produced bycontinuously feeding a dialkyl carbonate and an aromatic monohydroxycompound which are the starting material into the first continuousmulti-stage distillation column in which a catalyst is present, carryingout the reaction and the distillation simultaneously in the firstcolumn, continuously withdrawing a first column low boiling pointreaction mixture containing a produced alcohol from an upper portion ofthe first column in a gaseous form, continuously withdrawing a firstcolumn high boiling point reaction mixture containing a produced alkylaryl carbonate from a lower portion of the first column in a liquidform, continuously feeding the first column high boiling point reactionmixture into the second continuous multi-stage distillation column inwhich a catalyst is present, carrying out the reaction and thedistillation simultaneously in the second column, continuouslywithdrawing a second column low boiling point reaction mixturecontaining a produced dialkyl carbonate from an upper portion of thesecond column in a gaseous form, continuously withdrawing a secondcolumn high boiling point reaction mixture containing a produced diarylcarbonate from a lower portion of the second column in a liquid formwhile continuously feeding the second column low boiling point reactionmixture containing the dialkyl carbonate into the first continuousmulti-stage distillation column.

As described above, the starting material may contain the alcohol, thealkyl aryl carbonate and the diaryl carbonate that are reactionproducts, and reaction by-products such as an alkyl aryl ether and highboiling point compounds. Taking into consideration the equipment andcost required for separation and purification in other processes, whenactually implementing the present invention industrially, it ispreferable for the starting material to contain small amounts of suchcompounds.

In the present invention, when continuously feeding the dialkylcarbonate and the aromatic monohydroxy compound which are the startingmaterial into the first continuous multi-stage distillation column, thisstarting material may be fed into the first distillation column in aliquid form and/or a gaseous form from inlet(s) provided in one or moreof positions in the upper portion or the middle portion of the firstdistillation column below the gas outlet in the upper portion of thefirst distillation column. It is also preferable to feed a startingmaterial containing a large proportion of the aromatic monohydroxycompound into the first distillation column in a liquid form from aninlet provided in the upper portion of the first distillation column,and feed a starting material containing a large proportion of thedialkyl carbonate into the first distillation column in a gaseous formfrom an inlet provided in the lower portion of the first distillationcolumn above the liquid outlet in the lower portion of the firstdistillation column.

Moreover, in the present invention, the first column high boiling pointreaction mixture containing the alkyl aryl carbonate continuouslywithdrawn from the lower portion of the first continuous multi-stagedistillation column is continuously fed into the second continuousmulti-stage distillation column. Here, the first column high boilingpoint reaction mixture is preferably fed into the second distillationcolumn in a liquid form and/or a gaseous form from inlet(s) provided inone or more of positions in the upper portion or the middle portion ofthe second distillation column below the gas outlet in the upper portionof the second distillation column. Moreover, in the case of using, asthe second distillation column, a distillation column having a packingportion in the upper portion thereof and a tray portion in the lowerportion thereof, which is a preferable embodiment of the presentinvention, it is preferable for at least one position where an inlet isinstalled to be between the packing portion and the tray portion.Moreover, in the case that the packing comprise a plurality ofstructured packings, it is preferable for an inlet to be installed in aspace between the structured packings.

Moreover, in the present invention, it is also preferable to carry out areflux operation of condensing the gaseous component withdrawn from thetop of each of the first continuous multi-stage distillation column andthe second continuous multi-stage distillation column, and thenreturning some of this component into the upper portion of thatdistillation column. In this case, the reflux ratio for the firstcontinuous multi-stage distillation column is in a range of from 0 to10, and the reflux ratio for the second continuous multi-stagedistillation column is in a range of from 0.01 to 10, preferably 0.08 to5, more preferably 0.1 to 2. For the first continuous multi-stagedistillation column, not carrying out such a reflux operation (i.e.reflux ratio=0) is also a preferable embodiment.

In the present invention, the method of making the catalyst be presentin the first continuous multi-stage distillation column may be anymethod. In the case that the catalyst is a solid that is insoluble inthe reaction liquid, it is preferable for the catalyst to be fixedinside the column by, for example, being installed on a plate inside thefirst continuous multi-stage distillation column or being installed inthe form of a packing. In the case of a catalyst that dissolves in thestarting material or the reaction liquid, it is preferable to feed thecatalyst into the first distillation column from a position above themiddle portion of the first distillation column. In this case, thecatalyst liquid dissolved in the starting material or reaction liquidmay be introduced into the column together with the starting material,or may be introduced into the column from a different inlet to thestarting material. The amount of the catalyst used in the firstcontinuous multi-stage distillation column in the present inventionvaries depending on the type of catalyst used, the types and proportionsof the starting material compounds, and reaction conditions such as thereaction temperature and the reaction pressure. The amount of thecatalyst is generally in a range of from 0.0001 to 30% by weight,preferably 0.005 to 10% by weight, more preferably 0.001 to 1% byweight, based on the total weight of the starting material.

Moreover, in the present invention, the method of making the catalyst bepresent in the second continuous multi-stage distillation column may beany method. In the case that the catalyst is a solid that is insolublein the reaction liquid, it is preferable for the catalyst to be fixedinside the column by, for example, being installed on a plate inside thesecond continuous multi-stage distillation column or being installed inthe form of a packing. In the case of a catalyst that dissolves in thestarting material or the reaction liquid, it is preferable to feed thecatalyst into the second distillation column from a position above themiddle portion of the second distillation column. In this case, thecatalyst liquid dissolved in the starting material or reaction liquidmay be introduced into the column together with the starting material,or may be introduced into the column from a different inlet to thestarting material. The amount of the catalyst used in the secondcontinuous multi-stage distillation column in the present inventionvaries depending on the type of catalyst used, the types and proportionsof the starting material compounds, and reaction conditions such as thereaction temperature and the reaction pressure. The amount of thecatalyst is generally in a range of from 0.0001 to 30% by weight,preferably 0.005 to 10% by weight, more preferably 0.001 to 1% byweight, based on the total weight of the starting material.

In the present invention, the catalyst used in the first continuousmulti-stage distillation column and the catalyst used in the secondcontinuous multi-stage distillation column may be the same or different,but are preferably the same. More preferably, the same catalyst is usedin both columns, this catalyst being one that dissolves in the reactionliquid in both columns. In this case, the catalyst dissolved in the highboiling point reaction mixture in the first continuous multi-stagedistillation column is generally withdrawn from the lower portion of thefirst distillation column together with the alkyl aryl carbonate and soon, and fed into the second continuous multi-stage distillation columnas is; this is a preferable embodiment. If necessary, the catalyst canbe newly added into the second continuous multi-stage distillationcolumn.

The reaction times for the transesterification reactions carried out inthe present invention are considered to equate to the average residencetimes of the reaction liquids in the first continuous multi-stagedistillation column and the second continuous multi-stage distillationcolumn. Each of these reaction times varies depending on the form of theinternal in the distillation column and the number of stages, the amountof the starting material fed into the column, the type and amount of thecatalyst, the reaction conditions, and so on. The reaction time in eachof the first continuous multi-stage distillation column and the secondcontinuous multi-stage distillation column is generally in a range offrom 0.01 to 10 hours, preferably 0.05 to 5 hours, more preferably 0.1to 3 hours.

The reaction temperature in the first continuous multi-stagedistillation column varies depending on the type of the startingmaterial compounds used, and the type and amount of the catalyst. Thisreaction temperature is generally in a range of from 100 to 350° C. Itis preferable to increase the reaction temperature so as to increase thereaction rate. However, if the reaction temperature is too high, thenside reactions become liable to occur, for example production ofby-products such as an alkyl aryl ether increases, which is undesirable.For this reason, the reaction temperature in the first continuousmulti-stage distillation column is preferably in a range of from 130 to280° C., more preferably 150 to 260° C., yet more preferably 180 to 250°C.

The reaction temperature in the second continuous multi-stagedistillation column varies depending on the type of the startingmaterial compounds used, and the type and amount of the catalyst. Thisreaction temperature is generally in a range of from 100 to 350° C. Itis preferable to increase the reaction temperature so as to increase thereaction rate. However, if the reaction temperature is too high, thenside reactions become liable to occur, for example production ofby-products such as an alkyl aryl ether, and Fries rearrangementproducts of the starting material compounds and the produced alkyl arylcarbonate and diaryl carbonate, and derivatives thereof increases, whichis undesirable. For this reason, the reaction temperature in the secondcontinuous multi-stage distillation column is preferably in a range offrom 130 to 280° C., more preferably 150 to 260° C., yet more preferably180 to 250° C.

Moreover, the reaction pressure in the first continuous multi-stagedistillation column varies depending on the type of the startingmaterial compounds used and the composition of the starting material,the reaction temperature, and so on. The first continuous multi-stagedistillation column may be at any of a reduced pressure, normalpressure, or an applied pressure. The pressure at the top of the columnis generally in a range of from 0.1 to 2×10⁷ Pa, preferably 10⁵ to 10⁷Pa, more preferably 2×10⁵ to 5×10⁶ Pa.

The reaction pressure in the second continuous multi-stage distillationcolumn varies depending on the type of the starting material compoundsused and the composition of the starting material, the reactiontemperature, and so on. The second continuous multi-stage distillationcolumn may be at any of a reduced pressure, normal pressure, or anapplied pressure. The pressure at the top of the column is generally ina range of from 0.1 to 2×10⁷ Pa, preferably 10³ to 10⁶ Pa, morepreferably 5×10³ to 10⁵ Pa.

Note that the first continuous multi-stage distillation column maycomprise two or more of the distillation column. In this case, two ormore of the distillation column may be connected in series or inparallel. Two or more of the distillation column may also be connectedin combination of in series and in parallel.

Moreover, the second continuous multi-stage distillation column maycomprise two or more of the distillation column. In this case, two ormore of the distillation column may be connected in series or inparallel. Two or more of the distillation column may also be connectedin combination of in series and in parallel.

The material constituting each of the first continuous multi-stagedistillation column and the second continuous multi-stage distillationcolumn used in the present invention is generally a metallic materialsuch as carbon steel or stainless steel. In terms of the quality of thearomatic carbonates produced, stainless steel is preferable.

Hereinbelow, the present invention will be described in more detail withreference to the following Examples, but the present invention is notlimited to the following Examples.

EXAMPLES

Following is a more detailed description of the present invention withreference to Examples. However, the present invention is not limited tothe following Examples.

The halogen content was measured by means of an ion chromatographymethod.

Example 1

<First Continuous Multi-Stage Distillation Column 101>

A continuous multi-stage distillation column as shown in FIG. 1 havingL₁=3300 cm, D₁=500 cm, L₁/D₁=6.6, n₁=80, D₁/d₁₁=17, and D₁/d₁₂=9 wasused. In this Example, the sieve tray having the cross-sectional areaper hole being approximately 1.5 cm² and the number of holes beingapproximately 250/m² were used as the internal.

<Second Continuous Multi-Stage Distillation Column 201>

A continuous multi-stage distillation column as shown in FIG. 2 havingL₂=3100 cm, D₂=500 cm, L₂/D₂=6.2, n₂=30, D₂/d₂₁=3.85, and D₂/d₂₂=11.1was used. In this Example, as the internal, two sets of Mellapak (totalnumber of stages 11) were installed in the upper portion, and the sievetray having the cross-sectional area per hole being approximately 1.3cm² and the number of holes being approximately 250/m² were used in thelower portion.

<Reactive Distillation>

Diphenyl carbonate was produced by carrying out reactive distillationusing a apparatus in which the first continuous multi-stage distillationcolumn 101 and the second continuous multi-stage distillation column 201were connected together as shown in FIG. 3.

A starting material 1 containing phenol and dimethyl carbonate in aweight ratio of phenol/dimethyl carbonate=1.9 was introducedcontinuously in a liquid form at a flow rate of 50 ton/hr from an upperinlet 11 of the first continuous multi-stage distillation column 101. Onthe other hand, a starting material 2 containing dimethyl carbonate andphenol in a weight ratio of dimethyl carbonate/phenol=3.6 was introducedcontinuously in a gaseous form at a flow rate of 50 ton/hr from a lowerinlet 12 of the first continuous multi-stage distillation column 101.The molar ratio for the starting materials introduced into the firstcontinuous multi-stage distillation column 101 was dimethylcarbonate/phenol=1.35. The starting materials substantially did notcontain halogens (outside the detection limit for the ionchromatography, i.e. 1 ppb or less). Pb(OPh)₂ as a catalyst wasintroduced from the upper inlet 11 of the first continuous multi-stagedistillation column 101 such that a concentration thereof in thereaction liquid was approximately 100 ppm. Reactive distillation wascarried out continuously under conditions of a temperature at the bottomof the first continuous multi-stage distillation column 101 being 225°C. and a pressure at the top of the column being 7×10⁵ Pa. A firstcolumn low boiling point reaction mixture containing methanol, dimethylcarbonate, phenol and so on was continuously withdrawn in a gaseous formfrom the top 13 of the first column, was passed through a heat exchanger14, and was withdrawn at a flow rate of 34 ton/hr from an outlet 16. Onthe other hand, a first column high boiling point reaction mixturecontaining methyl phenyl carbonate, dimethyl carbonate, phenol, diphenylcarbonate, the catalyst and so on was continuously withdrawn in a liquidform from the bottom 17 of the first column.

A stable steady state was attained after 24 hours. The first column highboiling point reaction mixture was then fed continuously into the secondcontinuous multi-stage distillation column 201 at a flow rate of 66ton/hr from a starting material inlet 21 installed between the Mellapakand the sieve tray. The liquid fed into the second continuousmulti-stage distillation column 201 contained 18.2% by weight of methylphenyl carbonate and 0.8% by weight of diphenyl carbonate. Reactivedistillation was carried out continuously under conditions of atemperature at the bottom of the second continuous multi-stagedistillation column 201 being 210° C., a pressure at the top of thecolumn being 3×10⁴ Pa, and a reflux ratio being 0.3. It was possible toattain stable steady state operation after 24 hours. A second column lowboiling point reaction mixture containing 35% by weight of dimethylcarbonate and 56% by weight of phenol was continuously withdrawn fromthe top 23 of the second column, the flow rate at an outlet 26 being55.6 ton/hr. The second column low boiling point reaction mixture wascontinuously fed into the first continuous multi-stage distillationcolumn 101 from the inlet 11 and/or the inlet 12. At this time, theamounts of fresh dimethyl carbonate and phenol newly fed into the firstcontinuous multi-stage distillation column 101 were adjusted so as tomaintain the above-mentioned compositions and amounts of the startingmaterial 1 and the starting material 2, taking into consideration thecomposition and amount of the second column low boiling point reactionmixture.

A second column high boiling point reaction mixture containing 38.4% byweight of methyl phenyl carbonate and 55.6% by weight of diphenylcarbonate was continuously withdrawn from the bottom 27 of the secondcolumn. It was found that the amount of diphenyl carbonate produced perhour was 5.74 tons. The selectivity for the diphenyl carbonate based onthe phenol reacted was 98%.

Prolonged continuous operation was carried out under these conditions.The amounts of diphenyl carbonate produced per hour at 500 hours, 2000hours, 4000 hours, 5000 hours, and 6000 hours after attaining stablestate (excluding the diphenyl carbonate contained in the startingmaterial) were 5.74 tons, 5.75 tons, 5.74 tons, 5.74 tons, and 5.75 tonsrespectively, and the selectivities were 98%, 98%, 98%, 98%, and 98%respectively, and hence the operation was very stable. Moreover, thearomatic carbonates produced substantially did not contain halogens (1ppb or less).

Example 2

Reactive distillation was carried out under the following conditionsusing the same apparatus as in Example 1.

A starting material 1 containing phenol and dimethyl carbonate in aweight ratio of phenol/dimethyl carbonate=1.1 was introducedcontinuously in a liquid form at a flow rate of 40 ton/hr from the upperinlet 11 of the first continuous multi-stage distillation column 101. Onthe other hand, a starting material 2 containing dimethyl carbonate andphenol in a weight ratio of dimethyl carbonate/phenol=3.9 was introducedcontinuously in a gaseous form at a flow rate of 43 ton/hr from thelower inlet 12 of the first continuous multi-stage distillation column101. The molar ratio for the starting materials introduced into thefirst continuous multi-stage distillation column 101 was dimethylcarbonate/phenol=1.87. The starting materials substantially did notcontain halogens (outside the detection limit for the ionchromatography, i.e. 1 ppb or less). Pb(OPh)₂ as a catalyst wasintroduced from the upper inlet 11 of the first continuous multi-stagedistillation column 101 such that a concentration thereof in thereaction liquid was approximately 250 ppm. Reactive distillation wascarried out continuously under conditions of a temperature at the bottomof the first continuous multi-stage distillation column 101 being 235°C. and a pressure at the top of the column being 9×10⁵ Pa. A firstcolumn low boiling point reaction mixture containing methanol, dimethylcarbonate, phenol and so on was continuously withdrawn in a gaseous formfrom the top 13 of the first column, was passed through a heat exchanger14, and was withdrawn at a flow rate of 43 ton/hr from the outlet 16. Onthe other hand, a first column high boiling point reaction mixturecontaining methyl phenyl carbonate, dimethyl carbonate, phenol, diphenylcarbonate, the catalyst and so on was continuously withdrawn in a liquidform from the bottom 17 of the first column.

A stable steady state was attained after 24 hours. The first column highboiling point reaction mixture was then fed continuously into the secondcontinuous multi-stage distillation column 201 at a flow rate of 40ton/hr from the starting material inlet 21 installed between theMellapak and the sieve tray. The liquid fed into the second continuousmulti-stage distillation column 201 contained 20.7% by weight of methylphenyl carbonate and 1.0% by weight of diphenyl carbonate. Reactivedistillation was carried out continuously under conditions of atemperature at the bottom of the second continuous multi-stagedistillation column 201 being 205° C., a pressure at the top of thecolumn being 2×10⁴ Pa, and a reflux ratio being 0.5. It was possible toattain stable steady state operation after 24 hours. A second column lowboiling point reaction mixture was continuously withdrawn from the top23 of the second column, the flow rate at the outlet 26 being 33.3ton/hr.

The second column low boiling point reaction mixture was continuouslyfed into the first continuous multi-stage distillation column 101 fromthe inlet 11 and/or the inlet 12. At this time, the amounts of freshdimethyl carbonate and phenol newly fed into the first continuousmulti-stage distillation column 101 were adjusted so as to maintain theabove-mentioned compositions and amounts of the starting material 1 andthe starting material 2, taking into consideration the composition andamount of the second column low boiling point reaction mixture.

A second column high boiling point reaction mixture containing 35.5% byweight of methyl phenyl carbonate and 61.2% by weight of diphenylcarbonate was continuously withdrawn from the bottom 27 of the secondcolumn. It was found that the amount of diphenyl carbonate produced perhour was 4.1 tons. The selectivity for the diphenyl carbonate based onthe phenol reacted was 97%.

Prolonged continuous operation was carried out under these conditions.The amounts of diphenyl carbonate produced per hour at 500 hours, 1000hours, and 2000 hours after attaining stable steady state were 4.1 tons,4.1 tons, and 4.1 tons respectively, and the selectivities based on thereacted phenol were 97%, 97%, and 97% respectively, and hence theoperation was very stable. Moreover, the aromatic carbonates producedsubstantially did not contain halogens (1 ppb or less).

Example 3

Reactive distillation was carried out under the following conditionsusing the same apparatus as in Example 1 except that the cross-sectionalarea per hole of each of the sieve trays in the second continuousmulti-stage distillation column 201 was made to be approximately 1.8cm².

A starting material 1 containing phenol and dimethyl carbonate in aweight ratio of phenol/dimethyl carbonate=1.7 was introducedcontinuously in a liquid form at a flow rate of 86 ton/hr from the upperinlet 11 of the first continuous multi-stage distillation column 101. Onthe other hand, a starting material 2 containing dimethyl carbonate andphenol in a weight ratio of dimethyl carbonate/phenol=3.5 was introducedcontinuously in a gaseous form at a flow rate of 90 ton/hr from thelower inlet 12 of the first continuous multi-stage distillation column101. The molar ratio for the starting materials introduced into thefirst continuous multi-stage distillation column 101 was dimethylcarbonate/phenol=1.44. The starting materials substantially did notcontain halogens (outside the detection limit for the ionchromatography, i.e. 1 ppb or less). Pb(OPh)₂ as a catalyst wasintroduced from the upper inlet 11 of the first continuous multi-stagedistillation column 101 such that a concentration thereof in thereaction liquid was approximately 150 ppm. Reactive distillation wascarried out continuously under conditions of a temperature at the bottomof the first continuous multi-stage distillation column 101 being 220°C. and a pressure at the top of the column being 8×10⁵ Pa. A firstcolumn low boiling point reaction mixture containing methanol, dimethylcarbonate, phenol and so on was continuously withdrawn in a gaseous formfrom the top 13 of the first column, was passed through a heat exchanger14, and was withdrawn at a flow rate of 82 ton/hr from the outlet 16. Onthe other hand, a first column high boiling point reaction mixturecontaining methyl phenyl carbonate, dimethyl carbonate, phenol, diphenylcarbonate, the catalyst and so on was continuously withdrawn in a liquidform from the bottom 17 of the first column.

A stable steady state was attained after 24 hours. The first column highboiling point reaction mixture was then fed continuously into the secondcontinuous multi-stage distillation column 201 at a flow rate of 94ton/hr from the starting material inlet 21 installed between theMellapak and the sieve tray. The liquid fed into the second continuousmulti-stage distillation column 201 contained 16.0% by weight of methylphenyl carbonate and 0.5% by weight of diphenyl carbonate. Reactivedistillation was carried out continuously under conditions of atemperature at the bottom of the second continuous multi-stagedistillation column 201 being 215° C., a pressure at the top of thecolumn being 2.5×10⁴ Pa, and a reflux ratio being 0.4. It was possibleto attain stable steady state operation after 24 hours. A second columnlow boiling point reaction mixture was continuously withdrawn from thetop 23 of the second column, the flow rate at the outlet 26 being 81.7ton/hr. The second column low boiling point reaction mixture wascontinuously fed into the first continuous multi-stage distillationcolumn 101 from the inlet 11. At this time, the amounts of freshdimethyl carbonate and phenol newly fed into the first continuousmulti-stage distillation column 101 were adjusted so as to maintain theabove-mentioned compositions and amounts of the starting material 1 andthe starting material 2, taking into consideration the composition andamount of the second column low boiling point reaction mixture.

A second column high boiling point reaction mixture containing 35.5% byweight of methyl phenyl carbonate and 59.5% by weight of diphenylcarbonate was continuously withdrawn from the bottom 27 of the secondcolumn. It was found that the amount of diphenyl carbonate produced perhour was 7.32 tons. The selectivity for the diphenyl carbonate based onthe phenol reacted was 98%.

Prolonged continuous operation was carried out under these conditions.The amounts of diphenyl carbonate produced per hour at 500 hours, 1000hours, and 2000 hours after attaining stable steady state were 7.32tons, 7.33 tons, and 7.33 tons respectively, and the selectivities basedon the reacted phenol were 98%, 98%, and 98% respectively, and hence theoperation was very stable. Moreover, the aromatic carbonates producedsubstantially did not contain halogens (1 ppb or less).

INDUSTRIAL APPLICABILITY

The present invention is suitable as a specific process that enablesaromatic carbonates containing diaryl carbonate as a main product to beproduced with high selectivity and high productivity stably for aprolonged period of time on an industrial scale of not less than 1 tonper hour using two continuous multi-stage distillation columns from adialkyl carbonate and an aromatic monohydroxy compound.

1. A process for the production of an aromatic carbonate containing adiaryl carbonate as a main product from a dialkyl carbonate and anaromatic monohydroxy compound as a starting material, which comprisesthe steps of: (i) continuously feeding said starting material into afirst continuous multi-stage distillation column in which a catalyst ispresent; (ii) carrying out the reaction in said first column to producean alcohol and an alkyl aryl carbonate; (iii) continuously withdrawing afirst column low boiling point reaction mixture containing a producedalcohol from an upper portion of said first column in a gaseous formwhile continuously withdrawing a first column high boiling pointreaction mixture containing an alkyl aryl carbonate from a lower portionof said first column in a liquid form; (iv) continuously feeding saidfirst column high boiling point reaction mixture into a secondcontinuous multi-stage distillation column in which a catalyst ispresent and which is connected to said first column while carrying outthe reaction in said second column to produce a dialkyl carbonate and adiaryl carbonate; (v) continuously withdrawing a second column lowboiling point reaction mixture containing said produced dialkylcarbonate from an upper portion of said second column in a gaseous formwhile continuously withdrawing a second column high boiling pointreaction mixture containing said produced diaryl carbonate from a lowerportion of said second column in a liquid form; wherein (a) a molarratio of the dialkyl carbonate to the aromatic monohydroxy compound insaid starting material which is fed continuously into said firstcontinuous multi-stage distillation column is in a range of from 0.1 to10; (b) said first continuous multi-stage distillation column comprisesa structure having a pair of end plates above and below a cylindricaltrunk portion having a length L₁ (cm) and an inside diameter D₁ (cm),and having an internal with a number of stages n₁ thereinside, and has agas outlet having an inside diameter d₁₁ (cm) at the top of the columnor in an upper portion of the column near to the top, a liquid outlethaving an inside diameter d₁₂ (cm) at the bottom of the column or in alower portion of the column near to the bottom, at least one inletprovided in the upper portion and/or a middle portion of the columnbelow the gas outlet, and at least one inlet provided in the lowerportion of the column above the liquid outlet, wherein (1) said lengthL₁ (cm) satisfies the following formula (1),1500≦L₁≦8000  (1), (2) said inside diameter D₁ (cm) of the columnsatisfies the following formula (2),100≦D₁≦2000  (2), (3) a ratio of said length L₁ (cm) to said insidediameter D₁ (cm) of the column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3), (4) said number of stages n₁ satisfies the followingformula (4),20≦n₁≦120  (4), (5) a ratio of said inside diameter D₁ (cm) of thecolumn to said inside diameter d₁₁ (cm) of the gas outlet satisfies thefollowing formula (5),5≦D ₁ /d ₁₁≦30  (5), and (6) a ratio of said inside diameter D₁ (cm) ofthe column to said inside diameter d₁₂ (cm) of the liquid outletsatisfies the following formula (6),3≦D ₁ /d ₁₂≦20  (6); (c) said second continuous multi-stage distillationcolumn comprises a structure having a pair of end plates above and belowa cylindrical trunk portion having a length L₂ (cm) and an insidediameter D₂ (cm), and having an internal with a number of stages n₂thereinside, and has a gas outlet having an inside diameter d₂₁ (cm) atthe top of the column or in an upper portion of the column near to thetop, a liquid outlet having an inside diameter d₂₂ (cm) at the bottom ofthe column or in a lower portion of the column near to the bottom, atleast one inlet provided in the upper portion and/or a middle portion ofthe column below the gas outlet, and at least one inlet provided in thelower portion of the column above the liquid outlet, wherein (1) saidlength L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7), (2) said inside diameter D₂ (cm) of the columnsatisfies the following formula (8),100≦D₂≦2000  (8), (3) a ratio of the length L₂ (cm) to said insidediameter D₂ (cm) of the column satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9), (4) said number of stages n₂ satisfies the followingformula (10),10≦n₂≦80  (10), (5) a ratio of said inside diameter D₂ (cm) of thecolumn to said inside diameter d₂₁ (cm) of the gas outlet satisfies thefollowing formula (11),2≦D ₂ /d ₂₁≦15  (11), and (6) a ratio of said inside diameter D₂ (cm) ofthe column to said inside diameter d₂₂ (cm) of the liquid outletsatisfies the following formula (12),5≦D ₂ /d ₂₂≦30  (12).
 2. The process according to claim 1, whereindistillation is carried out simultaneously in said step (ii) and saidstep (iv).
 3. The process according to claim 1, wherein an amount ofsaid diaryl carbonate produced is not less than 1 ton per hour.
 4. In aprocess for the production of an aromatic carbonate containing a diarylcarbonate as a main product in which the aromatic carbonate containingthe diaryl carbonate as the main product are produced continuously bytaking a mixture of a dialkyl carbonate and an aromatic monohydroxycompound as a starting material, continuously feeding the startingmaterial into a first continuous multi-stage distillation column inwhich a catalyst is present, carrying out the reaction and thedistillation simultaneously said the first column, continuouslywithdrawing a first column low boiling point reaction mixture containinga produced alcohol from an upper portion of said first column in agaseous form, continuously withdrawing a first column high boiling pointreaction mixture containing a produced alkyl aryl carbonate from a lowerportion of said first column in a liquid form, continuously feeding thefirst column high boiling point reaction mixture into a secondcontinuous multi-stage distillation column in which a catalyst ispresent, carrying out the reaction and the distillation simultaneouslyin said second column, continuously withdrawing a second column lowboiling point reaction mixture containing a produced dialkyl carbonatefrom an upper portion of said second column in a gaseous form,continuously withdrawing a second column high boiling point reactionmixture containing a produced diaryl carbonate from a lower portion ofsaid second column in a liquid form while continuously feeding thesecond column low boiling point reaction mixture containing the dialkylcarbonate into the first continuous multi-stage distillation column, theimprovement in which: (a) a molar ratio of the dialkyl carbonate to thearomatic monohydroxy compound in said starting material which is fedcontinuously into said first continuous multi-stage distillation columnis in a range of from 0.1 to 10; (b) said first continuous multi-stagedistillation column comprises a structure having a pair of end platesabove and below a cylindrical trunk portion having a length L₁ (cm) andan inside diameter D₁ (cm), and having an internal with a number ofstages n₁ thereinside, and has a gas outlet having an inside diameterd₁₁ (cm) at the top of the column or in an upper portion of the columnnear to the top, a liquid outlet having an inside diameter d₁₂ (cm) atthe bottom of the column or in a lower portion of the column near to thebottom, at least one inlet provided in the upper portion and/or a middleportion of the column below the gas outlet, and at least one inletprovided in the lower portion of the column above the liquid outlet,wherein (1) said length L₁ (cm) satisfies the following formula (1),1500≦L₁≦8000  (1), (2) said inside diameter D₁ (cm) of the columnsatisfies the following formula (2),100≦D₁≦2000  (2), (3) a ratio of said length L₁ (cm) to said insidediameter D₁ (cm) of the column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3), (4) said number of stages n₁ satisfies the followingformula (4),20≦n₁≦120  (4), (5) a ratio of said inside diameter D₁ (cm) of thecolumn to said inside diameter d₁₁ (cm) of the gas outlet satisfies thefollowing formula (5),5≦D ₁ /d ₁₁≦30  (5), and (6) a ratio of said inside diameter D₁ (cm) ofthe column to said inside diameter d₁₂ (cm) of the liquid outletsatisfies the following formula (6),3≦D ₁ /d ₁₂≦20  (6); (c) said second continuous multi-stage distillationcolumn comprises a structure having a pair of end plates above and belowa cylindrical trunk portion having a length L₂ (cm) and an insidediameter D₂ (cm), and having an internal with a number of stages n₂thereinside, and has a gas outlet having an inside diameter d₂₁ (cm) atthe top of the column or in an upper portion of the column near to thetop, a liquid outlet having an inside diameter d₂₂ (cm) at the bottom ofthe column or in a lower portion of the column near to the bottom, atleast one inlet provided in the upper portion and/or a middle portion ofthe column below the gas outlet, and at least one inlet provided in thelower portion of the column above the liquid outlet, wherein (1) saidlength L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7), (2) said inside diameter D₂ (cm) of the columnsatisfies the following formula (8),100≦D₂≦2000  (8), (3) a ratio of the length L₂ (cm) to said insidediameter D₂ (cm) of the column satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9), (4) said number of stages n₂ satisfies the followingformula (10),10≦n₂≦80  (10), (5) a ratio of said inside diameter D₂ (cm) of thecolumn to said inside diameter d₂₁ (cm) of the gas outlet satisfies thefollowing formula (11),2≦D ₂ /d ₂₁≦15  (11), and (6) a ratio of said inside diameter D₂ (cm) ofthe column to said inside diameter d₂₂ (cm) of the liquid outletsatisfies the following formula (12),5≦D ₂ /d ₂₂≦30  (12).
 5. The process according to claim 4, wherein anamount produced of the diaryl carbonate is not less than 1 ton per hour.6. The process according to claim 1, wherein d₁₁ and d₁₂ satisfy thefollowing formula (13), and d₂₁ and d₂₂ satisfy the following formula(14)1≦d ₁₂ /d ₁₁≦5  (13)1≦d ₂₁ /d ₂₂≦6  (14).
 7. The process according to claim 1, wherein L₁,D₁, L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for said first continuous multi-stagedistillation column satisfy the following formulae: 2000≦L₁≦6000,150≦D₁≦1000, 3≦L₁/D₁≦30, 30≦n₁≦100, 8≦D₁/d₁₁≦25, and 5≦D₁/d₁₂≦18,respectively, and L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said secondcontinuous multi-stage distillation column satisfy the followingformulae: 2000≦L₂≦6000, 150≦D₂≦1000, 3≦L₂/D₂≦30, 15≦n₂≦60,2.5≦D₂/d₂₁≦12, and 7≦D₂/d₂₂≦25, respectively.
 8. The process accordingto claim 1, wherein, L₁, D₁, L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for saidfirst continuous multi-stage distillation column satisfy the followingformulae: 2500≦L₁≦5000, 200≦D₁≦800, 5≦L₁/D₁≦15, 40≦n₁≦90, 10≦D₁/d₁₁≦25,and 7≦D₁/d₁₂≦15, respectively, and L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂for said second continuous multi-stage distillation column satisfy thefollowing formulae: 2500≦L₂≦5000, 200≦D₂≦800, 5≦L₂/D₂≦15, 20≦n₂≦50,3≦D₂/d₂₁≦10, and 9≦D₂/d₂₂≦20, respectively.
 9. The process according toclaim 1, wherein each of said first continuous multi-stage distillationcolumn and said second continuous multi-stage distillation column is adistillation column having a tray and/or a packing as the internal. 10.The process according to claim 9, wherein said first continuousmulti-stage distillation column is a plate-type distillation columnhaving the tray as the internal, and said second continuous multi-stagedistillation column is a distillation column having both the packing andthe tray as the internal.
 11. The process according to claim 9, whereineach of the trays in said first continuous multi-stage distillationcolumn and said second continuous multi-stage distillation column is asieve tray having a sieve portion and a down corner portion.
 12. Theprocess according to claim 11, wherein said sieve tray has 100 to 1000holes/m² in the sieve portion.
 13. The process according to claim 11,wherein the cross-sectional area per hole of said sieve tray is in arange of from 0.5 to 5 cm².
 14. The process according to claim 9,wherein said second continuous multi-stage distillation column is adistillation column having, as said internal, the packing in an upperportion of the column, and the tray in a lower portion of the column.15. The process according to claim 1, wherein said packing of saidinternal in said second continuous multi-stage distillation column isone or more of a structured packing.
 16. The process according to claim15, wherein said structured packing in said second continuousmulti-stage distillation column is of at least one selected from thegroup consisting of Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, a Sulzerpacking, a Goodroll packing and a Glitchgrid.
 17. The process accordingto claim 1, wherein said first continuous multi-stage distillationcolumn comprises two or more of distillation columns.
 18. The processaccording to claim 1, wherein said second continuous multi-stagedistillation column comprises two or more of distillation columns. 19.An aromatic carbonate comprising a halogen content of not more than 0.1ppm, produced by the process according to claim
 1. 20. A reactivedistillation apparatus comprising a first continuous multi-stagedistillation column for carrying out reaction and distillation; and asecond continuous multi-stage distillation column for carrying outreaction and distillation, which is connected to said first continuousmulti-stage distillation column, comprising: (a) said first continuousmulti-stage distillation column comprises a structure having a pair ofend plates above and below a cylindrical trunk portion having a lengthL₁ (cm) and an inside diameter D₁ (cm), and having an internal with anumber of stages n₁ thereinside, and has a gas outlet having an insidediameter d₁₁ (cm) at the top of the column or in an upper portion of thecolumn near to the top, a liquid outlet having an inside diameter d₁₂(cm) at the bottom of the column or in a lower portion of the columnnear to the bottom, at least one inlet provided in the upper portionand/or a middle portion of the column below the gas outlet, and at leastone inlet provided in the lower portion of the column above the liquidoutlet, wherein (1) said length L₁ (cm) satisfies the following formula(1),1500≦L₁≦8000  (1), (2) said inside diameter D₁ (cm) of the columnsatisfies the following formula (2),100≦D₁≦2000  (2), (3) a ratio of said length L₁ (cm) to said insidediameter D₁ (cm) of the column satisfies the following formula (3),2≦L ₁ /D ₁≦40  (3),ps (4) said number of stages n₁ satisfies thefollowing formula (4),20≦n₁≦120  (4), (5) a ratio of said inside diameter D₁ (cm) of thecolumn to said inside diameter d₁₁ (cm) of the gas outlet satisfies thefollowing formula (5),5≦D ₁ /d ₁₁≦30  (5), and (6) a ratio of said inside diameter D₁ (cm) ofthe column to said inside diameter d₁₂ (cm) of the liquid outletsatisfies the following formula (6),3≦D ₁ /d ₁₂≦20  (6); (b) said second continuous multi-stage distillationcolumn comprises a structure having a pair of end plates above and belowa cylindrical trunk portion having a length L₂ (cm) and an insidediameter D₂ (cm), and having an internal with a number of stages n₂thereinside, and has a gas outlet having an inside diameter d₂₁ (cm) atthe top of the column or in an upper portion of the column near to thetop, a liquid outlet having an inside diameter d₂₂ (cm) at the bottom ofthe column or in a lower portion of the column near to the bottom, atleast one inlet provided in the upper portion and/or a middle portion ofthe column below the gas outlet, and at least one inlet provided in thelower portion of the column above the liquid outlet, wherein (1) saidlength L₂ (cm) satisfies the following formula (7),1500≦L₂≦8000  (7), (2) said inside diameter D₂ (cm) of the columnsatisfies the following formula (8),100≦D₂≦2000  (8), (3) a ratio of the length L₂ (cm) to said insidediameter D₂ (cm) of the column satisfies the following formula (9),2≦L ₂ /D ₂≦40  (9), (4) said number of stages n₂ satisfies the followingformula (10),10≦n₂≦80  (10), (5) a ratio of said inside diameter D₂ (cm) of thecolumn to said inside diameter d₂₁ (cm) of the gas outlet satisfies thefollowing formula (11),2≦D ₂ /d ₂₁≦15  (11), and (6) a ratio of said inside diameter D₂ (cm) ofthe column to said inside diameter d₂₂ (cm) of the liquid outletsatisfies the following formula (12),5≦D ₂ /d ₂₂≦30  (12).
 21. The reactive distillation apparatus accordingto claim 20, wherein d₁₁ and d₁₂ satisfy the following formula (13), andd₂₁ and d₂₂ satisfy the following formula (14)1≦d ₁₂ /d ₁₁≦5  (13)1≦d ₂₁ /d ₂₂≦6  (14).
 22. The reactive distillation apparatus accordingto claim 20, wherein L₁, D₁, L₁/D₁, n₁, D₁/d₁₁, and D₁/d₁₂ for saidfirst continuous multi-stage distillation column satisfy the followingformulae: 2000≦L₁≦6000, 150≦D₁≦1000, 3≦L₁/D₁≦30, 30≦n₁≦100, 8≦D₁/d₁₁≦25,and 5≦D₁/d₁₂≦18, respectively, and L₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂for said second continuous multi-stage distillation column satisfy thefollowing formulae: 2000≦L₂≦6000, 150≦D₂≦1000, 3≦L₂/D₂≦30, 15≦n₂≦60,2.5≦D₂/d₂₁≦12, and 7≦D₂/d₂₂≦25, respectively.
 23. The reactivedistillation apparatus according to claim 20, wherein L₁, D₁, L₁/D₁, n₁,D₁/d₁₁, and D₁/d₁₂ for said first continuous multi-stage distillationcolumn satisfy the following formulae: 2500≦L₁≦5000, 200≦D₁≦800,5≦L₁/D₁≦15, 40≦n₁≦90, 10≦D₁/d₁₁≦25, and 7≦D₁/d₁₂≦15, respectively, andL₂, D₂, L₂/D₂, n₂, D₂/d₂₁, and D₂/d₂₂ for said second continuousmulti-stage distillation column satisfy the following formulae:2500≦L₂≦5000, 200≦D₂≦800, 5≦L₂/D₂≦15, 20≦n₂≦50, 3≦D₂/d₂₁≦10, and9≦D₂/d₂₂≦20, respectively.
 24. The reactive distillation apparatusaccording to claim 20, wherein each of said first continuous multi-stagedistillation column and said second continuous multi-stage distillationcolumn is a distillation column having a tray and/or a packing as theinternal.
 25. The reactive distillation apparatus according to claim 24,wherein said first continuous multi-stage distillation column is aplate-type distillation column having the tray as the internal, and saidsecond continuous multi-stage distillation column is a distillationcolumn having both the packing and the tray as the internal.
 26. Thereactive distillation apparatus according to claim 24, wherein each ofthe trays in said first continuous multi-stage distillation column andsaid second continuous multi-stage distillation column is a sieve trayhaving a sieve portion and a down comer portion.
 27. The reactivedistillation apparatus according to claim 26, wherein said sieve trayhas 100 to 1000 holes/m² in the sieve portion.
 28. The reactivedistillation apparatus according to claim 26, wherein thecross-sectional area per hole of said sieve tray is in a range of from0.5 to 5 cm².
 29. The process according to claim 24, wherein said secondcontinuous multi-stage distillation column is a distillation columnhaving, as said internal, the packing in an upper portion of the column,and the tray in a lower portion of the column.
 30. The reactivedistillation apparatus according to claim 24, wherein said packing ofsaid internal in said second continuous multi-stage distillation columnis one or more of a structured packing.
 31. The reactive distillationapparatus according to claim 30, wherein said structured packing in saidsecond continuous multi-stage distillation column is of at least oneselected from the group consisting of Mellapak, Gempak, TECHNO-PAK,FLEXI-PAK, a Sulzer packing, a Goodroll packing and a Glitchgrid. 32.The reactive distillation apparatus according to claim 20, wherein saidfirst continuous multi-stage distillation column comprises two or moreof distillation columns.
 33. The reactive distillation apparatusaccording to claim 20, wherein said second continuous multi-stagedistillation column comprises two or more of distillation columns.